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ETRADCHEM Workshop 2017
23rd-24th March 2017. Villeurbanne, France
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2017 Workshop « Electron Transfer, Radical Ions and
Radical Chemistry ». March 23 and 24, 2017.
Université Lyon 1 Campus LyonTech – La Doua
ETRADCHEM Workshop 2017
23rd-24th March 2017. Villeurbanne, France
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On behalf of the organizing committee, I warmly welcome you to this first Workshop edition
that will focus on electron-transfer reactions and reactivity of radical ions and radicals.
The program spans a range of topics of radical and electron-transfer processes in organic
chemistry, electrochemistry, radical and electron-transfer induced polymerization processes,
photo-electrochemistry, photoredox catalysis, catalysis and theory.
This event will honor Professor John A. Murphy (University of Strathclyde, Glasgow, Scotland)
who is an invited Professor at the Université Claude Bernard Lyon 1 from March 22 to April 20,
2017.
I would like to express my sincere thanks to all members of the organizing committee for their
continuous and enthusiastic efforts. The cellule financière of the ICBMS is also acknowledged for
their help. I am also grateful to our generous institutional and industrial sponsors, who have made
this event possible.
I wish you all a very fruitful workshop and a pleasant stay in Lyon.
Maurice MEDEBIELLE
Organizing committee: Maurice Médebielle, Lionel Perrin, Paolo Larini and Anis Tlili.
Université Claude Bernard Lyon 1, ICBMS UMR 5246.
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GENERAL INFORMATION
Location
The workshop will take place at the CPE Lyon – Ecole Supérieure de Chimie Physique
Electronique de Lyon
Locate CPE building and Tramway stations LA DOUA GASTON BERGER and UNIVERSITE
LYON 1:
ETRADCHEM Workshop 2017
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To access the Université Claude Bernard Lyon 1 campus (La Doua) and location of the Workshop,
please use tramway lines T1 (bound to IUT Feyssine) or T4 (bound to La Doua-Gaston Berger,
Terminus) and get off at La Doua – Gaston Berger’s station. Both lines are connected to Part Dieu
Railway Station (20-22 minutes).
From Lyon Saint-Exupéry Airport, you can reach Part Dieu Railway Station using the Rhône-
Express Train: https://www.rhonexpress.fr/en
Transport
Local public transport: http://www.tcl.fr
ETRADCHEM Workshop 2017
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Internet
Wifi access will be provided during the Workshop
Working language
The working language of the workshop is English
SPONSORS
ETRADCHEM Workshop 2017
23rd-24th March 2017. Villeurbanne, France
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SCIENTIFIC PROGRAMME
Speakers
PLENARY LECTURE
John A. MURPHY (Glasgow, Scotland): Evolution of Organic Super Electron Donors
INVITED LECTURES
Samir ZARD (Ecole Polytechnique, Palaiseau): Radical-Polar Crossover: Manifold Implications
for Synthesis
Yannick LANDAIS (Université de Bordeaux, Bordeaux): Free-Radical Additions to Olefins.
Recent Developments and Applications
Laurence FERAY (Université d'Aix-Marseille, Marseille): α-Bromoacrylate as radical acceptor
in dialkylzincs-mediated radical-polar crossover processes, theoretical investigation and
synthetic applications
DAY 1 Thursday March 23 DAY 2 Friday March 24
8:30-9:10 Registration 8:30-8:55 Registration
9:15-9:30 Welcome 9:00-9:25 T. NOEL
9:30-10:00 J. A. MURPHY 9:30-9:55 B. KONIG
10:00-10:15 10:00-10:25 M. BRASHOLZ
10:20-10:45 S. ZARD 10:30-10:45 Break
10:50-11:15 Y. LANDAIS 10:50-11:15 M. E. BUDEN
11:20-11:45 L. FERAY 11:20-11:45 A. TLILI
11:50-12:15 C. OLLIVIER 11:50-12:15 M. PUIATTI
12:30-14:00 Lunch 12:30-14:00 Lunch
14:15-14:40 J. BROGGI 14:15-14:40 F. MASERAS
14:45-15:10 D. GIGMES 14:45-15:10 V. ROBERT
15:15-15:40 E. LACOTE 15:15-15:40 L. PERRIN
15:45-16:10 Break 15:45-16:10 Break
16:15-16:40 J. BONIN 16:15-16:45 Feedback
16:45-17:10 N. LE POUL 16:45-17:00 Farewell
17:15-17:40 C. BUCHER
17:45-18:10 M.-N. COLLOMB
19:45 Dîner
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Cyril OLLIVIER (Université Pierre et Marie Curie, Paris): Photoredox Catalysis for the
Generation of Carbon Centered Radicals and Synthetic Applications
Julie BROGGI (Université d’Aix-Marseille, Marseille): New horizons for Organic Electron
Donors
Didier GIGMES (Université d’Aix-Marseille, Marseille): Photopolymerization initiators:
Synthesis and photochemical studies
Emmanuel LACOTE (Université Lyon 1, Villeurbanne): Organic and Polymer Free-radical
Synthesis using NHC–Boranes
Julien BONIN (Université Paris Diderot, Paris): Molecular Catalysis of the Photochemical
Reduction of CO2 into CO and beyond: on the Road to Solar Fuels
Nicolas Le POUL (Université de Brest, Brest): Surface functionalization by model complexes of
copper enzymes: the “self-induced electroclick” approach
Christophe BUCHER (ENS Lyon, Lyon): Electron-triggered metamorphism in viologen-based
(supra)molecular materials
Marie-Noëlle COLLOMB (Université Grenoble Alpes, Grenoble): Photo-induced redox catalysis
for hydrogen production with molecular compounds
Timothy NOEL (TU Eindhoven, Pays-Bas): Engineering of photocatalytic reactions in
microreactors
Burkhard KONIG (Université de Regensburg, Allemagne): Visible light photoredox catalysis with
radical anions
Malte BRASHOLZ (Université d'Hambourg, Allemagne): New photoredox-induced cascade
reactions
Maria Eugenia BUDEN (Université Nationale de Cordoba, Argentine): Photoinduced Electron
Transfer in base-promoted Homolytic Aromatic Substitution and Related Systems. Is t-butoxide
anion a key ingredient?
Anis TLILI (Université Lyon 1, Villeurbanne): KOtBu promoted intermolecular cross-coupling
through electron transfer
Marcelo PUIATTI (Université Nationale de Cordoba, Argentine): “The Palme d'Or goes to ...".
A search for the best functional for dealing with anionic organic species
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Feliu MASERAS (Tarragone, ICIQ, Catalogne): Characterization of single electron steps in water
oxidation through DFT calculations
Vincent ROBERT (Université de Strasbourg, Strasbourg): Charge Transfer Processes: Prime
Role of Optimized Molecular Orbitals
Lionel PERRIN (Université Lyon 1, Villeurbanne): Exploring the reactivity of the Kagan’s
reagent from a theoretical perspective
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Evolution of Organic Super Electron Donors
J. A. Murphy
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL,
United Kingdom
My research group has been fortunate to develop a number of simple organic electron donors,
structurally related to enols, enolates and enamines; in this way, we have built upon the excellent
pioneering work of many people including Bunnett,1 Rossi2 and Narasaka.3
Our starting point was to ask whether a neutral organic ground state molecule could reduce an aryl
halide. The search for such a molecule led us to understand some of the factors that control the
power and selectivity of organic electron donors, and their scope as reducing agents.
Being coloured reagents, they readily absorb visible and near-UV light; this adds to their power as
donors, and allows them to tackle even more challenging synthetic tasks. This presentation will
give an overview of developments relating to these electron donors from our current perspective.
References
1. Scamehorn, R. G.; Bunnett, J. F. J. Org. Chem. 1977, 42, 14491457.
2. Guastavino, J. V.; Rossi, R. A. J. Org. Chem. 2012, 77, 460472.
3. Narasaka, K. Pure & Appl. Chem. 1997, 69, 601604.
-1,50E-05
-1,00E-05
-5,00E-06
0,00E+00
5,00E-06
1,00E-05
-2,5 -2 -1,5 -1 -0,5 0
Cu
rren
t/ A
Potential/ V
ETRADCHEM Workshop 2017
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Professor JOHN A. MURPHY
B.A. (Mod.), Ph.D., C. Chem., F.R.S.C., F.R.S.E.
CURRICULUM VITAE
http://www.johnmurphygroup.com/
1. Name: John Anthony Murphy Nationality: Irish
2. University Education:
1972-1976 University of Dublin.
Awarded B.A. (Moderatorship) First Class.
Awards Held: Department of Education Scholar (1972-1976).
University of Dublin Foundation Scholar (1974-1979). Goulding Scholar
(1975); Gold Medallist of the University (1976); Cocker Medallist for
Experimental Chemistry (1976).
1976-1979 University of Cambridge. (Hutchinson Research Studentship.)
Awarded Ph.D. in Organic Chemistry (with Prof. Jim Staunton)
3. Appointments Held:
2013-2016 Head of Department
2007-2012 Director, Glasgow Centre for Physical Organic Chemistry
2010- to date Head of Organic Chemistry
2007-2013 Deputy Head of Department
2006-2008 Director, WestCHEM
2004-2006 Deputy Director, WestCHEM
1995- to date Merck-Pauson Professor, University of Strathclyde.
1994-1995 Reader, University of Nottingham.
1983-1994 Lecturer, University of Nottingham.
1982-1983 College Lecturer, Jesus College, Oxford. .
1980-1983 Departmental Demonstrator, University of Oxford.
with Prof. J. E. Baldwin on bioorganic chemistry.
1979-1980 Izaak Walton Killam Fellowship, University of Alberta
4. International and National Recognition:
2017 Visiting Professor, Université Claude Bernard (Lyon- 1)
2016 The Charles Rees Award for Heterocyclic Chemistry (Royal Society of
Chemistry)
2013 Visiting Lectureship, University of Kyoto
2012 The Bader Award in Organic Chemistry (Royal Society of Chemistry)
2007 Visiting Fellow at the Australian National University.
2004 Visiting Professor, Université Pierre et Marie Curie, Paris
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2002 D.Sc. (University of Strathclyde)
2001 Presidential Visiting Professor, N.A.I.S.T., Japan.
2001 Elected Fellow of the Royal Society of Edinburgh
2001 Royal Society Leverhulme Senior Research Fellow
1999 Invited “Troisième Cycle” Lecturer, Switzerland.
1998 Elected Fellow of the Royal Society of Chemistry.
1996 Visiting Professor at l’Université d’Aix Marseille.
1995 Visiting Fellow at the Australian National University.
I am an organic chemist and my research group revels in exploring chemical reactivity in synthesis
and in biology. My research group website is http://www.johnmurphygroup.com/ We have a
particular interest in electron transfer reactions and in radical chemistry, but are generally interested
in mechanisms of organic reactions.
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Radical-Polar Crossover: Manifold Implications for Synthesis
S. Z. Zard
Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau, France.
Abstract. Our research group is mostly concerned with the discovery and development of new
reactions and processes that could be useful in organic synthesis. As is usually the case in scientific
research, the interplay between conjecture and chance observation underlies much of our work.
Unexpected events often bring a fresh lighting to the system being examined and open doors
hitherto unsuspected. Misconception has thus played an important role by allowing us to uncover
a number of new radical and non-radical reactions of some generality involving sulfur compounds,
acetylenes, oximes, and related derivatives: we simply followed the logical consequences of our
observations and went where the chemistry took us. In this lecture, the crossover from the radical
to the cationic manifold that can take place in some of these reactions will be presented and the
various mechanistic and synthetic implications discussed briefly.
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Samir Z. Zard
Personal: Date and place of birth: 18th June 1955, Ife (Nigeria)
Nationality: French Marital status: Married, two children
Professional Address: Laboratoire de Synthèse Organique, Ecole Polytechnique, 91128 Palaiseau,
France.
Phone: +33-1-69 33 59 71; Fax: +33-1-69 33 59 72; e-mail: [email protected]
Education:
1978 BSc : Imperial College of Science and Technology, London University (1st Class Honours).
ARCS (Associate of the Royal College of Science) 1st Class Honours.
Awards: Hofmann Prize; Edward Frankland Prize; Edmund White Prize
1983 PhD : Université Paris-Sud, Orsay, France (supervisor: Professor Sir Derek Barton).
Employment:
CNRS: 1981, Attaché de Recherche; 1983, Chargé de Recherche; 1989, Directeur de Recherche (2nd
Class); 1996, Directeur de Recherche (1st Class); 2003, Directeur de Recherche (Exceptional Class).
Ecole Polytechnique: 1986, Maître de Conférences (part- time); 2000, Full Professor (part-time).
Field of research: Discovery and mechanistic study of new reactions and processes.
Publications: 342; Patents: 37
Honors and distinctions:
* The 1992 Prize of the Organic Chemistry Division of the French Chemical Society.
* The 1995 Clavel-Lespiau Prize of the French Academy of Science.
* Chemistry Research Promotion Center of the National Science Council Fellow (Taiwan, 1997)
* Astra-Zeneca USA Lecturer 1999.
* Sherbrooke-Bohringer Ingelheim Canada Lecturer 2000
* Rhodia Prize 2000
* Bürgenstock Lecturer 2001
* Merck Sharpe & Dohme Lecturer 2003
* Chevalier des Palmes Académiques 2003
* Japan Society for the Promotion of Science Fellow 2004.
* Organic Syntheses Distinguished Lecturer 2005
* Novartis Chemistry Lectureship 2006-2007
* Inaugural Wyeth Lecturer 2006
* Prix Dargelos 2006
* President, Bürgenstock Conference 2007
* Silver Medal CNRS 2007
* Croix de Chevalier dans l’Ordre de la Légion d’Honneur 2007
* Novartis-UC Irvine Distinguished Lecturer 2008
* Novartis-Berkeley Distinguished Lecturer 2008
* Bristol-Myers Squibb-Scripps Institute Distinguished Lecturer 2008
* Prix de l’Innovation 2008 — Ecole Polytechnique
* Grignard-Wittig Award 2008 of the German Chemical Society
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* Woodward Lecturer, Harvard University 2010
* Bohringer Ingelheim-University of British Columbia Distinguished Lecturer 2010-2011
* Honorary Member of the Sociedad Argentina de Investigación en Química Orgánica, 2011
* Fellow of the Royal Society of Chemistry, 2011
* 1st Barton Lecturer in Creativity in Organic Synthesis (2012-Imperial College)
* Grand Prix Joseph-Achille Le Bel of the French Chemical Society, 2012
* Birch Lecturer, Australia National University, 2015
* Liversidge Lecturer, University of Sydney, 2015
* Elected Foreign Corresponding Member of the Academy of Sciences of Lisbon (Portugal), 2015
* Honorary Doctorate, American University of Beirut, 2016.
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Free-Radical Additions to Olefins. Recent Developments and Applications
Y. Landaisa
a Institute of Molecular Sciences, University of Bordeaux, UMR-CNRS-5255, 351 cours de la libération, 33405
Talence, France
The regioselective free-radical addition onto olefins has attracted a considerable interest as it gives
rise to useful intermediates for organic synthesis starting from readily available material.1 In this
context, our laboratory has developed three-component radical functionalization of olefins, relying
on the addition of two carbon fragments across the olefinic skeleton, providing adducts with two
new C-C bonds along with additional functional groups. Carbo-alkynylation and carbo-oximation
as well as carbo-aminomethylation were thus devised, using various olefinic partners and sulfones
as radical traps.2 More recently, we extended this chemistry to the development of a one-pot carbo-
alkenylation of olefins,3 as well as a useful carbo-cyanation.4 The scope and limitations of these
methodologies will be discussed, along with their application to the total synthesis of natural
alkaloids.5 Efforts towards the development of tin-free versions of these processes will also be
disclosed.
(1) Subramanian, H.; Landais, Y.; Sibi M. P. in Comprehensive Organic synthesis, Eds. G. A. Molander, P. Knochel,
2nd ed., Vol. 4, Oxford: Elsevier, 2014, pp. 699-741.
(2) (a) Godineau, E.; Landais, Y. J. Am. Chem. Soc. 2007, 129, 12662. (b) Liautard, V.; Robert, F.; Landais, Y. Org.
Lett. 2011, 13, 2658. (c) Ovadia, B.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 1958. (d) Landais, Y.; Robert,
F.; Godineau, E.; Huet, L.; Likhite, N. Tetrahedron 2013, 69, 10073. (e) Ovadia, B.; Robert, F.; Landais, Y.
Chimia, 2016, 70, 34.
(3) (a) Poittevin, C.; Liautard, V.; Beniazza, R.; Robert, F.; Landais, Y. Org. Lett. 2013, 15, 2814. (b) Beniazza, R.;
Liautard, V.; Poittevin, C.; Ovadia, B.; Mohammed, S.; Robert, F.; Landais, Y. Chem. Eur. J. 2017, 23, 2439.
(4) (a) Hassan, H.; Pirenne, V.; Wissing, M.; Chahinaz, K.; Hussain, A.; Robert, F.; Landais Y. Chem. Eur. J. 2017,
DOI: 10.1002/chem.201605946. (b) Dange, N. S.; Robert, F.; Landais, Y. Org. Lett. 2016, 18, 6156.
(5) Hassan, H.; Mohammed, S.; Robert, F.; Landais, Y. Org. Lett. 2015, 17, 4518.
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Prof. Yannick Landais Institute of Molecular Sciences (UMR-5255), University of Bordeaux 351, Cours de la libération, 33405 Talence, France Tel: (+33) 5 40 00 22 89; Fax: (+33) 5 40 00 62 86 Email: [email protected]
A. Personal Information Date of Birth: 09.01.1962 Place of Birth: Angers, France
B. Higher education and professional experience 1997- Professor of Organic Chemistry at the University of Bordeaux (F) 1990-97 Assistant-Professor (University of Lausanne, CH). 1994 Habilitation (University Paris-XI, Orsay, F). 1988-90 Postdoctoral fellow at the University of Cambridge (UK) with Prof. I. Fleming 1987-88 Military Service 1984-87 PhD thesis with Dr. J.-P. Robin, University Paris-XI-Orsay (F). "Recherche sur les voies d’accès aux
lignanes bisbenzocyclooctadiénes et aux alcaloïdes présentant la structure biarylique pontée".
C. Fellowships, Awards and Honors 2014 Prize of the Organic Chemistry Division of the French Chemical Society (http://www.societechimiquedefrance.fr/Chimie-organique-14.html) 2014 Fellow of the French Chemical Society (1st promotion) 2000-05 Junior Member of the "Institut Universitaire de France" 1997 Alfred Werner Prize of the New Swiss Chemical Society (https://scg.ch/award) 1988-90 EU Postdoctoral Fellowship (Cambridge, UK) 1984-87 PhD Fellowship from the French “Ministère de la Recherche et de l’Enseignement Supérieur“
D. Research Interests Organosilicon Chemistry, Radical and organometallic chemistry, Organocatalysis, Asymmetric synthesis, Synthesis of natural products. See also webpage: http://ylandais.free.fr
E. Metrics 127 publications in peer-reviewed journals, 10 book chapters, 2 patents.
F. Lectures in Universities and industries 70 lectures in universities 28 Lectures in national and international congresses.
G. Selected Administrative duties
2010-14 Member of the Scientific committee of the CNRS National Institute of Chemistry (INC) 2013- President of the French-Japanese Association of Chemistry 2015- Member of the International Advisory Board of “European Journal of Organic Chemistry”
H. Supervision
Supervision of 30 PhD thesis, 5 currently ongoing, and 13 post-doctoral researchers.
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α-Bromoacrylate as radical acceptor in dialkylzincs-mediated radical-polar
crossover processes, theoretical investigation and synthetic applications.
Laurence Feray,* Hugo Lingua, François Vibert, Julien Maury, Eric Besson, Didier Siri and
Michèle P. Bertrand
Aix Marseille Univ., CNRS, Institut de Chimie Radicalaire, UMR 7273, Equipes CMO and CT, Campus Saint-
Jérôme, Avenue Normandie-Niemen, 13397 Marseille Cedex 20, France
Under non-degassed medium ethyl -bromoacrylate reacts with diethylzinc to give a
bromocyclopropane. The reaction successively involves a radical addition followed by an SH2 at
zinc, conjugate addition of the resulting enolate to the electrophilic substrate and finally a ring
closure.[1] In the presence of t-butyl iodide the bromocyclopropane resulting from the addition of
t-butyl radical is formed.
Theoretical calculations were performed to get a better insight into the detailed mechanism. They
highlight the impact of zinc(II) chelation on the formal SH2 step.
[1] Vibert, F; Maury, J; Lingua, H; Besson, E; Siri, D; Bertrand, M.P.; Feray, L. Tetrahedron 2015, 71, 8991–9002
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Feray Laurence Professeur des Universités
Aix-Marseille Université, Institut de Chimie Radicalaire
Equipe CMO, Campus Saint-Jérôme, case 562, Marseille
33 (0)4 91 28 85 99 / 06 17 37 52 03
Education and scientific career
1996-2000 Ph. D. in Organic Chemistry under the direction of Pr Michèle Bertrand, Marseille. Thematic area:
Triethylborane and diethylzinc in radical reactions.
2000-2001 Post-doctoral position under the direction of Pr Philippe Renaud, Fribourg, Switzerland.
Thematic area : Diastereoselective 1,5-hydrogen atom transfer.
2001 Maître de conférences, Aix-Marseille Université (AMU)
2008 Habilitation à Diriger des Recherches (HDR), Marseille « Dialkylzincs in radical chemistry, synthetic
applications »
2015 Professeur, Aix-Marseille Université
Research :
Development of radical methodologies based on the use of organometallic reagents.
Dialkylzincs as promoters of radical-polar multicomponent reactions in aerobic medium, mechanistic studies and
synthetic applications (synthesis of -lactones, lactams, pyrrolizidines, stereocontrolled synthesis of olefines…)
Metal catalyzed carbozincation of various substrates
Training and administrative responsabilities in Aix-Marseille Université:
Manager of L2, L3 chemistry degree
Assistant Director, departement of chemistry
Keywords:
Radical chemistry, Organometallic chemistry, Dialkylzincs, Radical-polar cascades, Multicomponent reactions.
Selected recent publications
(a) J. Maury, L. Feray, P. Perfetti, M. P. Bertrand, Org. Lett. 12 (2010) 3590. (b) J. Maury, D. Mouysset, L. Feray, S.
R. A. Marque, D. Siri, M. P Bertrand, Chem. —Eur. J. 18 (2012) 3241. (c) J. Maury, L. Feray, M. P Bertrand, Org.
Lett. 13 (2011) 1884. (d) J. Maury, S. Jammi, F. Vibert, S. R. A. Marque, D. Siri, L. Feray, M. P. Bertrand, J. Org.
Chem. 77 (2012) 9081. (e) S. Jammi, D. Mouysset, D. Siri, M. P Bertrand, L. Feray, J. Org. Chem. 77 (2013) 1589.
(f) Vibert, F.; Maury, J.; Lingua, H.; Besson, E.; Siri, D.; Bertrand, M. P.; Feray, L. Tetrahedron 2015, 71, 8991-9002.
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Photoredox Catalysis for the Generation of Carbon Centered Radicals
and Synthetic Applications
C. Ollivier
UPMC Univ-Paris 06 – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR CNRS 8232)
4 Place Jussieu, C. 229, 75005 Paris, France
Visible-light photoredox catalysis has emerged as a valuable and a greener alternative to generate
radicals by single electron transfer reactions from an appropriate photocatalyst - which can be a
polypyridine complex of transition metal or an organic dye - that absorbs light in the visible region.
Since the pioneering studies of Kellogg, Pall and Deronzier, important contributions have been
reported for synthetic purposes. In this context, we investigated various radical transformations1
involving photoreduction of ketoepoxides, ketoaziridines, onium salts and O-thiocarbamates. We
took advantage of the reactivity of the photogenerated radicals to create new carbon-carbon bonds
and related mechanistic studies were performed. Our next endeavors concerned the photocatalyzed
oxidation of stabilized carbanions such 1,3-dicarbonyl enolates and more extensively bis-
catecholato silicates. Because of their low oxidation potentials, the later have proved to be exquisite
sources of radical entities which can be engaged in diverse intermolecular reactions such as
vinylation, alkynylation and conjugate additions. The bis-catecholato silicates were also shown to
behave as excellent partners of dual photoredox-nickel dual catalysis leading in an expeditious
manner to libraries of cross coupling products.
1 For an account of this work, see: Goddard, J.-P.; Ollivier, C.; Fensterbank, L. Acc. Chem. Res. 2016, 49, 1924.
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Cyril OLLIVIER
CNRS Research Director
PhD and Habilitation Diploma (HDR) in Organic Chemistry
Université Pierre et Marie Curie – Sorbonne Universités, Institut Parisien de Chimie Moléculaire (UMR 8232), 4, Place Jussieu. Case 229. Tour 32-42, 5ème étage, pièce 516, 75252 Paris Cedex 05. France
Tel. ++33 (0)1 44 27 38 50 Fax ++33 (0)1 44 27 73 60, [email protected] http://www.ipcm.fr/OLLIVIER-Cyril
EDUCATION AND DIPLOMAS Habilitation Diploma (HDR) – Accreditation to supervise research June 2013 Pierre and Marie Curie University – Sorbonne University, Paris, France Ph.D. in Organic Chemistry - Doctor rerum naturalium December 2000 joint degree at the University of Fribourg, Fribourg, Switzerland and Pierre and Marie Curie University, Paris, France Thesis Title: Development of efficient and practical radical processes for the formation of carbon-carbon and carbon-heteroatom bonds B.S.; M.S. in Chemistry June 1995 Pierre and Marie Curie University, Paris, France Research Interests in Master: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement
CURRENT POSITION Pierre and Marie Curie University – Sorbonne University, Paris, France October 2016 – present CNRS Research Director Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry
PREVIOUS POSITIONS Pierre and Marie Curie University, Paris, France January 2007 – September 2016 CNRS Research Fellow 1st class (Chargé de recherche) Research Interests: Development of new directions for research on synthetic radical and organometallic chemistry Aix-Marseille University, Marseille, France October 2002 – December 2006 CNRS Research Fellow 2nd class (then 1st class in October 2006) Research Interests: Reactivity of allylsilanes and synthesis of steroids, particularly vitamin D analogs University of Texas at Austin, Austin, TX January 2001 – September 2002
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SNSF and NIH Postdoctoral fellow Advisor: Prof. Philip D. Magnus Research Interests: Approaches to the total synthesis of the diterpene antibiotic guanastepene University of Fribourg, Fribourg, Switzerland October 1996 – December 2000 and Pierre and Marie Curie University, Paris, France Graduate Student (Swiss National Science Foundation (SNSF)) Advisors: Prof. Philippe Renaud and Prof. Max Malacria Research Interests: Organoboranes as a source of radicals, radical oxygenation and azidation Ecole Nationale Supérieure de Techniques Avancées, Paris, France October 1995 – September 1996 Scientific Associate in Organic Chemistry Advisor: Cmdr. Dr. Laurent El Kaim Research Interests: Diazo esters addition to trifluoropyruvamides Pierre and Marie Curie University, Paris, France October 1994 – June 1995 Master Student Advisors: Prof. Jean-François Normant and Dr. Fabrice Chemla Research Interests: Reactivity of hemithioketals as carbenoïds in 1,2 metallate rearrangement
CURRENT RESEARCH INTERESTS Organic Synthesis Methods and Concepts. Radical Synthetic Chemistry. Organometallic Catalysis for Synthesis. Asymmetric catalysis. Eco-friendly Synthesis. Multi-step Synthesis Green Radical Synthesis: Methods and Development of New Cascade Processes ➢ N−Acylcyanamides as new partners for radical cascade reactions. Synthesis of polyheterocyclic
nitrogen-containing compounds ➢ Electron Transfert Reactions
• Use of Titanium(IV) and Iron(II) complexes as new radical mediators • Development of visible-light photoredox catalysis for the generation of radicals
Transition metal catalyzed cyclization and cycloisomerisation ➢ Chiral counteranions in asymmetric catalysis
PUBLICATIONS AND BIBLIOMETRIC DATA 70 Research publications 7 Book chapters 15 International and national lectures, seminars and oral communications 35 Posters
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New horizons for Organic Electron Donors
J. Broggi*
Aix Marseille Univ, CNRS, ICR Institut de Chimie Radicalaire, Faculté de Pharmacie, Marseille, France
The astonishing recent advances of their reactivities in fundamental organic chemistry have raised
a real interest for reducing agents with totally organic neutral structures and exceptionally negative
redox potentials.1 Strong organic electron donors (OEDs) are capable of single- or double-electron
transfer to organic substrates under mild and homogeneous conditions, promoting bond formations
through the generation of radical or anionic intermediates. Major contributions have been made in
this field demonstrating the efficiency of OEDs in the selective reduction of challenging chemical
bonds.2 The OEDs thus represent serious rivals to highly aggressive metal-based reducers and
emerge as an attractive novel source of reducing electrons in many aspects.
Despite a great tunability, approaches involving OED-promoted electron transfers have been
under-exploited, limiting the visibility of academic and industrial applications. Their convenience
of manipulation and storage is still hampered by several technical parameters that could dissuade
chemists of their usage. In order to extend their functionalities, our research primarily focus on the
development of new methodologies, essential to outline the potential of organic electron donors.
Our recent results in the development of masked OED-systems and the exploration of
unprecedented applications in the field of material science will be presented.3
1For reviews, see: a) Broggi, J.; Terme, T.; Vanelle, P. Angew. Chem. Int. Ed. 2014, 53, 384. b) Murphy, J. A. In
Encyclopedia of Radicals in Chemistry, Biology and Materials; Chatgilialoglu, C., Studer, A., Eds.; WILEY-VCH,
Weinheim, 2012. c) Zhou, S.; Farwaha, H.; Murphy, J. A. Chimia 2012, 66, 418. d) Murphy, J. A. J. Org. Chem. 2014,
79, 3731. e) Doni, E.; Murphy, J. A. Chem. Commun. 2014, 50, 6073. 2 a) Cahard, E.; Schoenebeck, F.; Garnier, J.; Cutulic, S. P. Y.; Zhou, S.; Murphy, J. A. Angew. Chem., Int. Ed. 2012,
51, 3673. b) Farwaha, H. S.; Bucher, G.; Murphy, J. A. Org. Biomol. Chem. 2013, 11, 8073. c) Doni, E.; O’Sullivan,
S.; Murphy, J. A. Angew. Chem. Int. Ed. 2013, 52, 2239. d) Doni, E.; Mondal, B.; O’Sullivan, S.; Tuttle, T.; Murphy,
J. A. J. Am. Chem. Soc. 2013, 135, 10934. e) Hanson, S. S.; Richard, N. A.; Dyker, C. A. Chem. Eur. J. 2015, 21, 8052.
f) Hanson, S. S.; Doni, E.; Traboulsee, K. T.; Coulthard, G.; Murphy, J. A.; Dyker, C. A. Angew. Chem. Int. Ed. 2015,
54, 11236. 3 Broggi, J.; Rollet, M.; Clément, J.L.; Canard, G.; Terme, T.; Gigmes, D.; Vanelle P. Angew. Chem. Int. Ed. 2016,
55, 5994. b) Rayala, R.; Giuglio-Tonolo, A.; Broggi, J.; Terme, T.; Vanelle, P.; Theard, P.; Médebielle, M.; Wnuk, S. F.
Tetrahedron 2016, 72, 1969.
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BROGGI Julie
Born: June 6th 1982
in Cannes, Alpes Maritimes
Nationality: French Current Position
Maître de Conférences (Lecturer) at the Organic Chemistry Department (Faculty of Pharmacy, AMU)
Institut de Chimie Radicalaire (ICR) - UMR 7273, Equipe Pharmacochimie radicalaire (PCR), 27 Bd Jean
Moulin, 13385 Marseille Cedex 5.
+33 (0)4 9183 5996 / [email protected]
Professional Experience
2010-2011 ATER (teaching assistant) - Laboratoire Chimie Provence (LCP), UMR 6264, Faculty of
Pharmacy, Aix-Marseille II.
Title: Super Electron Donors as tools in the synthesis of new nucleosidic analogues.
2009 Post-doctoral position – S. P. Nolan group Research school of chemistry, St Andrews,
United Kingdom.
Title: European project (EuMet): Development and application in catalysis of ruthenium
complexes bearing an N-heterocyclic carbene.
2005-2008 Ph.D. - Institut de Chimie Organique et Analytique (ICOA), UMR 6005, Faculty of
Science, Orléans.
Title: Contribution of N-heterocyclic carbene-containing catalysts in the nucleoside
chemistry. (Advisor: Prof. L.A. Agrofoglio and Dr. S. Bertaina-Raboin)
2005 Master training course - Laboratoire de Chimie des Molécules BioActives et des Arômes
(LCMBA), UMR 6001, Faculty of Science, Nice.
Title: Synthesis of a new AZT prodrug.
Research interests
JB is involved in the synthesis of novel organic reducers and their stable latent precursors. She also explores
their reactivity in the reduction of uninvestigated species and for unprecedented applications including
nucleoside or polymer chemistry. She is experienced in organic and medicinal compound synthesis, as well
as coordination chemistry and organometallic catalysis. She is used to perform air- and moisture-sensitive
experiments and handle unstable products.
Scientific Publications
19 publications in peer-review journals including 3 contributions to monographs, 3 oral communications
and 18 poster presentations.
• Polymerization initiated by organic electron donors J. Broggi,* M. Rollet, J.-L. Clément, G. Canard, T. Terme, D. Gigmes, P. Vanelle* Angew. Chem. Int. Ed.
2016, 55, 5994-5999.
• Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine
derivatives R. Rayala, A. Giuglio-Tonolo, J. Broggi, T. Terme, P. Vanelle, P. Theard, M. Médebielle,* S. F. Wnuk*
Tetrahedron, 2016, 72, 1969-1977.
• Organic electron donors as powerful single-electron reducing agents in organic synthesis
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J. Broggi,* T. Terme,* P. Vanelle* Angew. Chem. Int. Ed. 2014, 53, 384-413.
• The isolation of [Pd{OC(O)H}(H)(NHC)(PR3)] (NHC = N-heterocyclic carbene) and its role in alkene
and alkyne reductions using formic acid
J. Broggi, V. Jurcík, O. Songis A. Poater, L. Cavallo, A. M. Z. Slawin, C. S. J. Cazin*J. Am. Chem. Soc.
2013, 135, 4588-4591.
• Novel antiviral C5-substituted pyrimidine acyclic nucleoside phosphonates selected as human
thymidylate kinase substrates D. Topalis, U. Pradère, V. Roy, C. Caillat, A. Azzouzi, J. Broggi, R. Snoeck, G. Andrei, J. Lin, S. Eriksson,
J. A. C. Alexandre, C. El-Amri, D. Deville-Bonne, P. Meyer, J. Balzarini, L. A. Agrofoglio* J. Med. Chem.
2011, 54, 222-232.
Julie Broggi, received her M.Sc. in organic chemistry from the Université de Nice Sophia-Antipolis
(France) in 2005 and then completed her Ph.D. on nucleoside chemistry in 2009 under the supervision of
Prof. Luigi Agrofoglio at the Université d’Orléans (France). Her Ph.D. work focused on the applications of
transition-metal complexes in the synthesis of nucleoside derivatives, such as triazolo-carbanucleosides and
phosphononucleosides. These potential smallpox inhibitors were synthesized in racemic or enantioselective
series. During this Ph.D., she spent some time as visiting fellow in the group of Prof. Steven P. Nolan at the
Institute of Chemical Research of Catalonia (Spain). She studied the contribution of copper and palladium
complexes, bearing N-heterocyclic carbene ligand, in cycloaddition, N-arylation or transfer hydrogenation
reactions. For the study of their mechanism of action, she used NMR spectroscopy at variable temperature
and isotopic-labelling experiments.
Early 2009, she moved to the School of Chemistry of the University of St Andrews (UK) to continue
working with Prof. Nolan as post-doctoral fellow. She worked on the synthesis of imidazolium salts and the
corresponding free carbenes along with the synthesis of ruthenium catalysts and their applications in
metathesis reactions. In the context of a metathesis European network (project EUMET - CP-FP 211468-
2), she supervised the training of junior group members.
In 2010, she was appointed ATER and then Maître de Conférences (Lecturer) in the PCR group of the
Institut de Chimie Radicalaire (ICR). She is involved in the synthesis of novel organic electron donors
and their stable latent precursors. These new organic reducers are used as powerful and selective alternative
tools to metallic derivatives in reduction strategies through single- or double-electron transfers. she also
explores their reactivity in the reduction of uninvestigated functional groups and for unprecedented
applications including nucleoside or polymer chemistry.
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Photopolymerization initiators: Synthesis and photochemical studies
D. Gigmes
Aix Marseille Univ, CNRS, Institut de Chimie Radicalaire, Marseille, France
Nowadays, photoinitiated polymerization is one of the preferred techniques for a large range of
applications such as coatings, inks and adhesives, dentistry, microelectronics, laser direct imaging
technology and 3D printing.1-3 Indeed, photopolymerization presents several advantages such as
fast polymerization kinetics even at room temperature, the absence of solvents limiting the
formation of volatile organic compounds and the possibility to irradiate with high precision specific
zones allowing the construction of tailored patterns. However, the employment of UV light,
generally required for this technique, remains a major issue due to its high energy and the toxicity
of the associated irradiation sources. To overcome this drawback, photoinitiating systems able to
initiate polymerization under soft light irradiation sources is currently the subject of intense
efforts.3 In this context, recently we have synthesized a large library of photosensitive molecules
based on naphthalimide and diketopyrrolopyrrole derivatives exhibiting for some of them a
remarkable effiency to initiate the polymerization under soft irradiation sources.4,5 Hence, in this
communication, the synthesis and the polymerization abilities of the most relevant prepared
compounds as well as their photochemical behaviour will be presented.
References
1. Fouassier, J. P.; Lalevee, J. Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency; Wiley-VCH:
Weinheim, Germany, 2012.
2. Dadashi-Silab, S.; Doran, S.; Yagci, Y. Chem. Rev. 2016, 116, 10212–10275.
3. Xiao, P.; Zhang, J.; Dumur, F.; Tehfe, M. A.; Morlet-Savary, F.; Graff, B.; Gigmes, D.; Fouassier, J. P.; Lalevée,
J. Prog. Polym. Sci. 2015, 41, 32-66.
4. Zhang, J.; Zivic, N.; Dumur, F.; Xiao, P.; Graff, B.; Fouassier, J. P.; Gigmes, D.; Lalevée, J. Polymer, 2014, 55,
6641-6972.
5. Zivic, N.; Bouzrati-Zerrelli, M.; Villotte, S.; Morlet-Savary, F.; Dietlin, C.; Dumur, F.; Gigmes, D.; Fouassier,
J.P.; Lalevée, J. Polym. Chem. 2016, 7, 5873-5879.
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Didier Gigmes completed his PhD in organic chemistry in 1998 under the
supervision of Prof. Paul Tordo at the University Paul Cézanne in Marseille
(France). Then he moved to Elf Atochem North America in Pennsylvania (King
of Prussia, PA, USA) to work as a post-doc in the field of controlled radical
polymerization using cobalt derivatives. In 2001, he was recruited as researcher
at CNRS to develop the nitroxide-mediated polymerization (NMP) technique. In
2008, he defended his Habilitation at the University of Provence (Marseille,
France) and in October 2010, he was appointed Research Director at the CNRS
working at Aix-Marseille University (Marseille, France). Currently, with his research group his main
concerns are focused on the development and use of new methodologies for the synthesis of advanced
polymer materials. He is also involved in the development of original methodologies for Nitroxide Mediated
Photopolymerization and the synthesis of versatile photo-initiators. DG is (co)author of 270 peer review
articles in international journals, 15 patents, 10 book chapters and editor of one book on NMP. In 2013, he
was awarded by the Société Chimique de France as « Junior Distinguinshed Member ».
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Organic and Polymer Free-radical Synthesis using NHC–Boranes
E. Lacôte;a D. P. Curran;b J. Lalevéec; M. Lansalotd and E. Bourgeat-Lami,d
aCNRS, Université Claude Bernard Lyon 1, Villeurbanne, France bUniversity of Pittsburgh (PA), USA
cENSCMu, Université de Haute-Alsace, Mulhouse, France dCNRS, CPE Lyon, Villeurbanne, France
Complexation of boron with N-Heterocyclic carbenes stabilizes boryl radicals and makes them
planar -type radicals. This has important consequences for the reactivity of NHC-borane
complexes. The radical stabilization ensures that they can be introduced in organic free-radical
synthesis and the donation makes the NHC-boryl radicals nucleophilic.
In the talk we will show that NHC-boranes are exquisite reagents for organic reactions and
photopolymerization in organic and disperse media.
• S.-H. Ueng, M. Makhlouf Brahmi, É. Derat, L. Fensterbank, E. Lacôte, M. Malacria, D. P. Curran, J. Am. Chem.
Soc. 2008, 130, 10082-10083, DOI: 10.1021/ja804150k.
• S. Telitel, A.-L. Vallet, S. Schweizer, B. Delpech, N. Blanchard, F. Morlet-Savary, B. Graff, D. P. Curran, M. Robert,
E. Lacôte, J. Lalevée, J. Am. Chem. Soc. 2013, 135, 16938-16947, DOI: 10.1021/ja4066267
• S. Telitel, A.‐L. Vallet, D. M. Flanigan, B. Graff, F. Morlet‐Savary, T. Rovis, J. Lalevée, E. Lacôte, Chem. Eur. J.
2015, 21, 13772-13777, DOI: 10.1002/chem.201500499.
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Emmanuel Lacôte
EDUCATION AND EMPLOYMENT
2015-present : University of Lyon, Univ. Claude Bernard Lyon 1, (department for hydrazines and polynitrogen energetic compounds), Villeurbanne ; Chair. 2013 : promoted directeur de recherche 1st class, CNRS. 2012 : University of Lyon, CPE Lyon, (department for chemistry, catalysis, polymers and processes), Villeurbanne. 2011 : appointed group leader, Inst. de chimie des subst. naturelles (CNRS), Gif s/ Yvette.
2008 : promoted directeur de recherche 2nd class, CNRS. 2004 : promoted chargé de recherche 1st class, CNRS. 2004 : Habilitation, Université Pierre et Marie Curie, defended September 27. 2000 : appointed chargé de recherche 2nd class, CNRS, U. Pierre et Marie Curie, Paris. 1999-2000 : Postdoctoral fellow, Stanford University, USA (Paul A. Wender). Total Synthesis of
Bryostatin 1 Analogs. 1999 : Ph. D. (joint degree), Université Pierre et Marie Curie / Université de Fribourg (Switzerland),
Advisors: Max Malacria, Philippe Renaud. Applications of Lewis acids in radical chemistry. Defended June 29, 1999.
1991-1995 : undergraduate studies, École Normale Supérieure, Paris
AWARDS
2016 : Bessel Award for research, Alexander v. Humboldt Foundation (Germany) 2012 : JSPS fellow (Chuo University, Tokyo, Japan) 2010 : Scholar in residence, Center of Excellence of the School of Sciences, Tokyo (Japan) 2010 : Excellence in research award, CNRS (PES, first call, renewed 2015). 2009 : Actelion Chair (ENSC Mulhouse) 2003 : Young investigator travel award, 38th Conference on Stereochemistry, Bürgenstock, Suisse 1999 : Lavoisier postdoctoral fellowship (French governement, declined), Cancer research fund award.
INVITED POSITIONS
• 2016: Queen's University, Kingston (ON, Canada) • 2014: Osaka Prefecture University (Japan) • 2012: Westfälische Wilhelms-Universität Münster (Germany) • 2010: University of Tokyo (Japan) • 2010: ENSCMu (France)
5 REPRESENTATIVE PUBLICATIONS
1) "Grafting of Secondary Diol-Amides onto [P2W15V3O62]9– Generates Hybrid Heteropoly Acids" Lachkar, D.; Vilona, D.; Dumont, E.; Lelli, M.; Lacôte, E. Angew. Chem. Int. Ed. 2016, 55, 5961-5965; DOI: 10.1002/anie.201510954. 2) "Polyboramines: Polymers featuring Lewis Pairs in their backbone for Hydrogen Release" Ledoux, A.; Larini, P.; Boisson, C.; Monteil, V.; Raynaud, J.; Lacôte, E. Angew. Chem. Int. Ed. 2015, 54, 15744-15749; DOI: 10.1002/anie.201508395. VIP paper (top 5% Angewandte accepted manuscripts). 3) "Formation of NHC-Boryl Radicals through Electrochemical and Photochemical Cleavage of the B–S bond in N-Heterocyclic Carbene-Boryl Sulfides" Telitel, S.; Vallet, A.-L.; Schweizer, S.; Delpech, B.; Blanchard, N.; Morlet-Savary, F.; Graff, B.; Curran, D. P.; Robert, M.; Lacôte, E.; Lalevée, J. J. Am. Chem. Soc. 2013, 135, 16938-16947; DOI: 10.1021/ja4066267.
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4) "NHC-Boranes Accelerate Type I Radical Photopolymerizations and overcome Oxygen Inhibition" Lalevée, J.; Telitel, S.; Tehfe, M.-A.; Fouassier, J. P.; Curran, D. P.; Lacôte, E. Angew. Chem. Int. Ed. 2012, 51, 5958-5961. 5) "Complexes of Borane and N-Heterocyclic Carbenes (NHC Boranes): A New Class of Radical Hydrogen Atom Donor" Ueng, S.-H.; Makhlouf Brahmi, M.; Derat, É.; Fensterbank, L.; Lacôte, E.; Malacria, M.; Curran, D. P. J. Am. Chem. Soc. 2008, 130, 10082-10083.
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Molecular Catalysis of the Photochemical Reduction of CO2 into CO
and beyond: on the Road to Solar Fuels
J. Bonin,* H. Rao and M. Robert
Université Paris Diderot, Sorbonne Paris Cite, Laboratoire d’Electrochimie Moléculaire
UMR 7591 CNRS, 15 rue Jean-Antoine de Baïf, 75205, Paris Cedex 13
Facing the current environmental and energy issues, the activation of small molecules such as
water, oxygen and carbon dioxide represents a main research challenge.1 In particular, the
generation of solar fuels, namely hydrogen, carbon monoxide, methane or methanol, using
catalysts made of abundant and non-toxic materials and with a minimum energy input is a long
term strategic objective.
To efficiently convert electrons into chemical energy stored in molecular bonds, either by
electrochemical or photochemical ways, processes require a selective and robust catalysis, which
necessitates its intimate understanding at the molecular scale.
In this presentation, I will present both fundamental and applied studies developed at LEM on
the use of molecular homogeneous catalysts based on fourth-period transition metals (Fe, Co, Ni),
and in particular iron porphyrins,2 to catalyze the photochemical reduction of CO2 into CO,3-6 and
beyond.7
(1) Tatin, A.; Bonin, J.; Robert, M. ACS Energy Lett. 2016, 1, 1062.
(2) Bonin, J.; Maurin, A.; Robert, M. Coord. Chem. Rev. 2016, DOI: 10.1016/j.ccr.2016.09.005.
(3) Bonin, J.; Chaussemier, M.; Robert, M.; Routier, M. ChemCatChem 2014, 6, 3200.
(4) Bonin, J.; Robert, M.; Routier, M. J. Am. Chem. Soc. 2014, 136, 16768.
(5) Chen, L.; Guo, Z.; Wei, X.-G.; Gallenkamp, C.; Bonin, J.; Anxolabéhère-Mallart, E.; Lau, K.-C.; Lau, T.-C.;
Robert, M. J. Am. Chem. Soc. 2015, 137, 10918.
(6) Rao, H.; Bonin, J.; Robert, M. Submitted.
(7) Bonin, J.; Schmidt, L. C.; Rao, H.; Robert, M. Submitted.
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Dr. Julien BONIN Associate Professor of Chemistry
Université Paris Diderot
Laboratoire d'Electrochimie Moléculaire – UMR 7591
15 Rue Jean-Antoine de Baïf
75205 Paris Cedex 13, France
Tel: (33) 1 57 27 87 93
Fax: (33) 1 57 27 87 88
http://www.lemp7.cnrs.fr/
Academic background
2016 / Habilitation à Diriger des Recherches.
June 2012 / Invited scientist, Instituto de Investigaciones en Fisico-química, Universidad Nacional de
Córdoba, Argentina.
December 2011 / Invited scientist, Ångström Laboratory, Uppsala University, Sweden.
Mai-June 2010 / Invited scientist, Department of Chemistry, Massachusetts Institute of Technology,
USA.
Since Sept. 2006 / Associate Professor of Chemistry, LEM, Université Paris Diderot.
2005-2006 / Postdoctoral Research Associate, Radiation Laboratory, of Notre Dame, USA.
2002-2005 / PhD in Molecular Physical Chemistry, Laboratoire de Chimie Physique, Université Paris
Sud 11.
Bibliographic records
26 publications
Research themes
Fundamental approaches of photochemical processes
Proton-coupled electron transfers
Photoinduced electron transfers and bond-breaking
Small molecule activation such as CO2 and protons reduction
Recent publications
1) Rao, H., Bonin, J. & Robert, M. “Non-sensitized Selective Photochemical Reduction of CO2 to CO under
Visible Light with an Iron Molecular Catalyst”, Chem. Commun. 53, 2830-3, 2017.
2) Bonin, J., Maurin, A. & Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical
Reduction of CO2 with Fe and Co Metal Based Complexes. Recent Advances”, Coord. Chem. Rev. 334,
184-98, 2017.
3) Tatin, A., Bonin, J. & Robert, M., “A Case for Electrofuels”, ACS Energy Lett. 1, 1062-4, 2016.
4) Rao, H., Yu, W.-Q., Zheng, H.-Q., Bonin, J., Fan, Y.-T., Hou, H.-W., “Highly Efficient Photocatalytic
Hydrogen Evolution from Nickel Quinolinethiolate Complexes under Visible Light Irradiation”, J. Power
Sources 324, 253-60, 2016.
5) Chen, L., Guo, Z., Wei, X.-G., Gallenkamp, C., Bonin, J., Anxolabehere-Mallart, E., Lau, K.-C., Lau, T.-
C. and Robert, M., “Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with
Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal
Center”, J. Am. Chem. Soc. 137, 10918-21, 2015.
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Surface functionalization by model complexes of copper enzymes: the “self-
induced electroclick” approach
N. Le Poula,*
aLaboratoire CEMCA, UMR CNRS 6521, Université de Bretagne Occidentale, Brest, France
The immobilization of biomimetic redox devices onto solid supports is of particular importance for
the development of efficient sensors and catalysts. It also raises the fundamental question of
coupled electron transfer to reactivity at a metal center. An appealing strategy to address this issue
is to graft a metal center in a well pre-organized and controlled way, such as in self-assembled
monolayers (SAMs). In this context, we have developed a procedure based on the self-induced
electrochemical immobilization of Cu complexes onto pre-modified gold electrodes through a
Cu(I)-catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition (“electroclick” reaction).1 Several
molecular and supramolecular biomimetic complexes have been successfully grafted according to
this approach.2-3 Two types of applications have been tested: catalytic reduction of nitrite ions4 and
selective detection of alkylamines5 (Figure) in an aqueous medium.
References
1. Gomila, A.; Le Poul, N.; Cosquer, N.; Kerbaol, J. M.; Noel, J. M.; Reddy, M. T.; Jabin, I.; Reinaud, O.;
Conan, F.; Le Mest, Y., Dalton Trans. 2010, 39 (48), 11516-11518.
2. Orain, C.; Le Poul, P.; Le Mest, Y.; Le Poul, N., J. Electroanal. Chem. 2013, 710, 48-58.
3. Orain, C.; Le Poul, N.; Gomila, A.; Kerbaol, J. M.; Cosquer, N.; Reinaud, O.; Conan, F.; Le Mest, Y., Chem.
Eur J. 2012, 18 (2), 594-602.
4. Orain, C.; Porras-Gutiérrez, A. G.; Evoung Evoung, F.; Charles, C.; Cosquer, N.; Gomila, A.; Conan, F.; Le
Mest, Y.; Le Poul, N., Electrochem. Commun. 2013, 34, 204-207.
5. De Leener, G.; Evoung-Evoung, F.; Lascaux, A.; Mertens, J.; Porras-Gutierrez, A. G.; Le Poul, N.; Lagrost,
C.; Over, D.; Leroux, Y. R.; Reniers, F.; Hapiot, P.; Le Mest, Y.; Jabin, I.; Reinaud, O.,. J. Am. Chem. Soc. 2016, 138
(39), 12841-12853.
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Nicolas LE POUL (born 1975)
CNRS Researcher (CR1) since 2006, Laboratory CEMCA UMR 6521 CNRS, University of Brest [email protected]; Web page (UBO)
EDUCATION
Master degree (1998), University of Rennes (FR)
Ph.D thesis (2001), University of Exeter (UK)
EXPERIENCES
Ph.D Thesis in Physical Chemistry (2001)“Charge transfer at the HTSC/liquid electrolyte interface” (University of Exeter (UK), Dr. S.J. Green)
Post-doctoral assistant (2002). “Ions sensors based on cathode phosphate materials”(University of Amiens (FR), UMR CNRS 6007, Pr J.-M. Tarascon)
Post-doctoral assistant (2004). “Electrochemical studies of synthetic models of copper enzymes” (University of Brest (FR), UMR CNRS 6521, Dr. Y. Le Mest)
Research engineer (2005). “Post-mortem studies of Li-ion batteries” (BATSCAP-BOLLORE (FR))
RESEARCH AREA
Electrochemistry of inorganic complexes and organic species ; Spectroelectrochemistry; Cryo-spectroelectrochemistry, Surface functionalization; Electrocatalysis.
SCIENTIFIC ACTIVITY
40 publications in international journals with peer view; Yearly participation to international meetings (oral communication).
SELECTED PUBLICATIONS
• "Immobilization of monolayers incorporating Cu funnel complexes onto gold electrodes. Application to the selective electrochemical recognition of primary alkylamines in water", G. De Leener, F. Evoung−Evoung, A. Lascaux, J. Mertens, A. G. Porras−Gutiérrez, N. Le Poul, C. Lagrost, D. Over, Y. R. Leroux, F. Reniers, P. Hapiot, Y. Le Mest, I. Jabin, O. Reinaud, J. Am. Chem. Soc. 2016, 138, 12841−12853.
• "Room−temperature characterization of a mixed−valent µ−hydroxodicopper(II,III)", J. A. Isaac, F. Gennarini, I. Lopez, A. Thibon−Pourret, R. David, G. Gellon, B. Gennaro, C. Philouze, F. Meyer, S. Demeshko, Y. Le Mest, M. Reglier, H. Jamet, N. Le Poul, C. Belle, Inorg. Chem. 2016, 55, 8263−8266.
• "Supramolecular modeling of mono-copper enzyme active sites with calix[6]arene-based funnel complexes", N. Le Poul, Y. Le Mest, I. Jabin, O. Reinaud, Acc. Chem. Res. 2015, 48, 2097-2106.
• "Electrochemically and chemically induced redox processes in molecular machines", N. Le Poul, B. Colasson , ChemElectrochem 2015, 2, 475-496.
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• "Electrocatalytic reduction of nitrite ions by a copper complex attached as SAMs on gold by “self-induced electroclick”: Enhancement of the catalytic rate by surface coverage decrease", C. Orain, A. G. Porras-Gutiérrez, F. Evoung Evoung, C. Charles, N. Cosquer, A. Gomila, F. Conan, Y. Le Mest, N. Le Poul, Electrochem. Commun. 2013, 34, 204-207.
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Electron-triggered metamorphism in viologen-based
(supra)molecular materials
C. Kahlfussa, E. Saint-Amanb, E. Dumonta and C. Buchera *
aUniv Lyon, Ens de Lyon, CNRS UMR 5182, Université Claude Bernard Lyon 1, Laboratoire de Chimie, F69342,
Lyon, France. bUniversité Grenoble-Alpes, CNRS, Département de Chimie Moléculaire (UMR 5250), F38400, Grenoble, France.
The ability to control the structure and organization of molecular materials has emerged in the past
decade as a major scientific objective that is mainly motivated by exciting foreseeable applications
in nanoscience. Enormous technologic interests are for instance at stake in being able to devise
molecular objects that could respond to external stimuli by changes in structure and function. These
particular properties can lead to applications in various domains as (i) in molecular electronics, (ii)
in analytic science, with switchable hosts allowing the controlled binding/release of pollutants or
drugs, (iii) in materials science with the development of adaptive supramolecular polymers.
In this lecture, the syntheses and detailed physico-chemical properties of a series of switchable
molecular architectures whose movements can be triggered by electrochemically driven self-
assembly of organic radicals will be presented.1-8 Particular emphasis will be given to electron-
responsive tweezer-like molecules allowing to control the organization within self-assembled
coordination oligomers/polymers. The dynamic properties of these redox-responsive molecular
architectures and molecular materials will mainly be discussed on the basis of electrochemical,
spectroelectrochemical and ESR experiments supported by quantum chemical calculations.
References
(1) Kahlfuss, C.; Saint-Aman, E.; Bucher, C. “Redox-controlled intramolecular motions triggered by -dimerization
and pimerization “ In Organic Redox Systems: Synthesis, Properties, and Applications; Nishinaga, T., Ed.; John Wiley
and sons, 2016.
(2) Iordache, A.; Oltean, M.; Milet, A.; Thomas, F.; Baptiste, B.; Saint-Aman, E.; Bucher, C. J. Am. Chem. Soc. 2012,
134, 2653.
(3) Iordache, A.; Kanappan, R.; Métay, E.; Duclos, M.-C.; Pellet-Rostaing, S.; Lemaire, M.; Milet, A.; Saint-Aman,
E.; Bucher, C. Org. Biomol. Chem. 2013, 11, 4383.
(4) Kahlfuss, C.; Métay, E.; Duclos, M.-C.; Lemaire, M.; Milet, A.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2014,
21, 2090; ibid C. R. Chimie 2014, 17, 505.
(5) Kahlfuss, C.; Milet, A.; Wytko, J. ; Weiss, J.; Saint-Aman, E.; Bucher, C. Org. Lett., 2015, 17 , 4058.
(6) Iordache, A.; Retegan, M.; Thomas, F.; Royal, G.; Saint-Aman, E.; Bucher, C. Chem. Eur. J. 2012, 18, 7648.
(8) Kahlfuss, C.; Denis-Quanquin, S.; Calin, N.; Dumont, E.; Garavelli, M.; Royal, G.; Cobo, S.; Saint-Aman, E.;
Bucher, C. J. Am. Chem. Soc. 2016, 138, 15234.
-ne
+ne
n
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Dr. Christophe Bucher, 45 years old, obtained a Ph.D. in Physical chemistry from the University of Burgundy at Dijon in 1999 (supervisor: Dr. Jean Michel Barbe). His thesis work involved investigations on the catalytic properties of iron and cobalt cyclam complexes. He was then Postdoctoral Fellow with Professor Jonathan Sessler at the University of Texas at Austin from Nov.1999 to Sept. 2001 working on pyrrole-based macrocycles and cryptands for applications in anion sensing. He started his academic career in 2001 as a CNRS researcher at the University Joseph Fourier-Grenoble in the Laboratory of Organic Electrosynthesis and Redox Photochemistry which became in 2005 the Department of Molecular Chemistry. In 2008 he obtained a HDR diploma delivered by the University of Grenoble. He joined the Ecole Normale Supérieure in Lyon in 2012 where he currently develops his own research activity as a senior CNRS researcher (http://www.ens-lyon.fr/CHIMIE/). He has a fully pluridisciplinary background with expertise ranging from organic synthesis, coordination chemistry and supramolecular chemistry to advanced physical chemistry including molecular/analytical electrochemistry and surface modification. His current fields of interest cover different aspects of supramolecular chemistry, including the design, synthesis and applications of electron-switchable molecular and supramolecular materials with particular emphasis on molecular hosts featuring e-switchable recognition properties and on e-responsive self-assembled supramolecular materials. Since 2004, he has been involved in teaching electrochemistry at ENS-Lyon at the undergraduate and postgraduate levels. He is also involved since 2012 as an expert in molecular electronics for the “Observatoire des Micro et Nanotechnologies (OMNT). Since 2014, he is member of the scientific board of the institute of chemistry in Lyon (ICL) and member of the local board of the French Chemical Society (SCF, Section Rhône-Alpes).
FIELDS OF INTEREST & EXPERTISE
Supramolecular Chemistry & Electrochemistry – Switchable Molecular and Supramolecular Materials – Molecular Machinery – Host-Guest Chemistry – Redox Activation and Sensing . PUBLICATION METRICS/AWARDS
C. Bucher is author or co-author of two book chapters, one patent and of more than 80 articles in peer reviewed international journals. ORCID ID : orcid.org/0000-0003-1803-6733 He has received in 2011 the Young researcher award from the French division of the International Society of Electrochemistry.
CHRISTOPHE BUCHER, PhD Research Director at the National Council for Scientific Research. Department of Chemistry “Supramolecular and Biorganic Chemistry” Group Ecole Normale Supérieure de Lyon [email protected] SCF membership N°: 26545 Tel : +(0033) 472 728 864 ; Fax : +(0033) 472 728 860
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Photo-induced redox catalysis for hydrogen production with molecular
compounds
M.-N. Collomb;a* R. Gueret;a C. E. Castillo;a T. Stoll;a J. Chauvin,a F. Odobel,b M. Sliwa,c P.
Lainé,d and J. Fortagea
a Université Grenoble Alpes, CNRS, DCM, UMR 5250, F-38000 Grenoble, France bUniversité Nantes, Univ LUNAM, CEISAM, CNRS,UMR 6230, F-44322 Nantes 3, France
cUniversité Lille 1, CNRS, LASIR, UMR 8516, 59655 Villeneuve d’Asq, France dUniversité Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS, 15 rue J-A de Baïf, 75013 Paris, France
Solar driven water-splitting into hydrogen and oxygen, also referred as artificial photosynthesis,
has emerged as a very attractive sustainable approach to produce the fuel H2. Molecular approaches
to generate H2 photochemically typically involve the association of three-components, a light-
harvesting antenna (photosensitizer), a H2-evolving catalyst, and a sacrificial electron donor in
homogeneous solution.1 If a large number of such photocatalytic systems have been reported, very
few of them are able to operate in pure aqueous solution, without co-organic solvent, because of
the lower stability/solubility of molecular compounds in water. However, this is an important
requirement for their further applications in photoelectrochemical water-splitting devices. This talk
will present our efficient systems for the visible-light-driven H2 production in water using rhodium2
and cobalt3 complexes as catalysts and [Ru(bpy)3]2+ as photosensitizer in the presence of ascorbate
as sacrificial electron donor. The advantages of
coupling catalyst and photosensitizer by a covalent
bond will be also presented as well as our promising
results towards the development of systems only
based on earth abundant elements by using a new
water soluble organic dye which represents a very
attractive alternative to [Ru(bpy)3]2+.
Acknowledgments: The authors wish to thank for financial supports the LABEX ARCANE (ANR-11-LABX-0003-
01) for the project H2Photocat and the French National Research Agency for the project HeteroCop (ANR-09-BLAN-
0183-01). This work was also supported by COST CM1202 program (PERSPECT H2O). 1 (a) Stoll, T.; Castillo, C. E.; Kayanuma, M.; Sandroni, M.; Daniel, C.; Odobel, F.; Fortage, J.; Collomb, M.-N., Coord. Chem. Rev., 2015, 304–
305, 20-37. (b) Queyriaux, N.; Kaeffer, N.; Morozan, A.; Chavarot-Kerlidou, M.; Artero V., J. Photochem. Photobiol. C: Photochem. Rev., 2015,
25, 90-105. 2 (a) Stoll, T.; Gennari, M.; Serrano, I.; Fortage, J.; Chauvin, J.; Odobel, F.; Rebarz, M.; Poizat, O.; Sliwa, M.; Deronzier A.; Collomb M.-N., Chem. Eur. J., 2013, 19, 782-792. (b) Stoll, T.; Gennari, M.; Fortage, J.; Castillo, C. E.; Rebarz, M.; Sliwa, M.; Poizat, O.; Odobel, F.;
Deronzier A.; Collomb, M.-N., Angew. Chem., Int. Ed. Engl., 2014, 53, 1654-1658. 3 (a) Varma, S.; Castillo, C. E.; Stoll, T.; Fortage, J.; Blackman, A. G.; Molton, F.; Deronzier A.; Collomb, M.-N. PhysChemChemPhys, 2013, 15, 17544-17552. (b) Gimbert-Surinach, C.; Albero, J.; Stoll, T.; Fortage, J.; Collomb, A. Deronzier, E. Palomares and A. Llobet, J. Am. Chem. Soc.,
2014, 136, 7655-7661. (c) R. Gueret, C. E. Castillo, M.-N.; Rebarz, M.; Thomas, F.; Hargrove, A.-A.; Pécaut, J.; Sliwa, M.; Fortage J.; Collomb
M.-N., J. Photochem. Photobiol., B, 2015, 152, Part A, 82-94.
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Marie-Noëlle COLLOMB
Marie-Noëlle Collomb, 50 ys. old, is Research Director 2nd class at the CNRS. She is the leader of the group
«Artificial photosynthesis and energy carriers» in the Chimie Inorganique Rédox laboratory (CIRE) at the
Département of Chimie Moléculaire (DCM), Université Grenoble Alpes. She received her Ph. D. from the
Université Joseph Fourier (UJF) of Grenoble in 1993 under the supervision of Alain Deronzier, in the field
of electrocatalytic carbon dioxide reduction with ruthenium carbonyl complexes. After a year working in
the group of Prof. Marc Fontecave on alkanes oxidation catalysis as lecturer at UJF (1993-94), she joined
the CNRS in 1994 as research scientist at UJF. In 1998-99, as a CNRS research associate (NATO
fellowship), she joined the groups of Profs R. H. Crabtree and G. W. Brudvig at Yale University (New
Haven, USA) to develop bioinspired manganese complexes for water oxidation. She was appointed CNRS
Research Director in 2007. Her background ranges from coordination chemistry, electrochemistry and
photo-induced redox catalysis. Her current research interest deals with the development of electrocatalytic
and photocatalytic systems based on transition metal complexes and recently on (oxide) metallic
nanoparticles for artificial photosynthesis applications (H2 production by water reduction and water
oxidation) in homogeneous and in heterogeneous phase (surface modified electrodes, semi-conductor based
photocathodes and photoanodes).
She has supervised 10 PhD thesis, 10 post-doctoral and more than 30 undergraduate and graduate fellows.
She is the author of 101 publications (h-index: 32, (ISI WEB of Knowledge)), two patents, 1 encyclopedia
chapter, and had more than 30 invitations in national and international conferences
(conferences/keynotes/lectures) and in Universities. She is and has been involved as coordinator and partner
in several national and international programs (ANRs (JCJC, blanche), Arcane Labex, CNRS-CONICYT and
ECOS Sud-CONICYT (Chili), Hubert Curien (New-zealand)…). She is also involved as a partner in a COST
ACTION CM1202 « PERSPECT-H2O: Supramolecular photocatalytic water-splitting” and member of the
GDR solar fuels. She has fruitful national and international collaborations (Germany (MPI for Chemical
Energy Conversion, Mulheïm, F.Neese, S. DeBeer, D. Pantazis), Spain (ICIQ Tarragona, A. Llobet, Univ.
of Girona, M. Romero), New-Zealand (Univ. of Auckland, A. G. Blackman), Chili (Univ. of Conception,
B. Luis RIVAS)). She also assumes different responsibilities, e.g. member of the Scientific Council of the
French ANR program "CES06 - Chemistry" (2014), member of the Scientific Council of the French LABEX
program ARCANE (since 2012), member of the Council of the Institute of Molecular Chemistry of
Grenoble (2012-2016) and of the DCM (since 2016), expert for research agencies.
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Engineering of photocatalytic reactions in microreactors
Timothy Noël*
*Eindhoven University of Technology, Micro Flow Chemistry & Process Technology, Eindhoven, The Netherlands.
Photoredox catalysis is emerging as a new and powerful tool in synthetic organic chemistry to
facilitate photochemical reactions by means of visible light.[1] Notable examples involve the use of
ruthenium(II)polypyridine complexes which upon irradiation produce a photoexcited state. This
photoexcited state gives rise to a single electron transfer process (SET) with organic substrates
which can undergo subsequently a synthetic transformation. Whereas a myriad of different
reactions have recently succumbed to this mode of catalysis, it is important to note that several
challenges still remain with respect to high catalyst loadings, extended reaction times, scalability,
and generality of the catalyst system.
In this oral communication, we will report on the acceleration of gas-liquid photocatalytic reactions
in continuous photomicroreactors.[2] We will go into detail on both engineering and
chemical/catalytic aspects of continuous-flow photochemistry. Relevant examples from our group
will be detailed on during the presentation.[3] Also, we will report on the development of a solar
photomicroreactor, which allows the efficient harvesting of solar energy for photocatalytic
transformations.[4]
[1] For some general reviews on photoredox catalysis: (a) D. M. Schultz and T. P. Yoon, Science, 2014, 343, 1239176.
(b) N. A. Romero and D. A. Nicewicz, Chem. Rev., 2016, 116, 10075-10166. (c) C. K. Prier, D. A. Rankic and D. W.
C. MacMillan, Chem. Rev., 2013, 113, 5322-5363.
[2] For reviews on continuous-flow photochemical processes: (a) D. Cambie, C. Bottecchia, N. J. W. Straathof, V.
Hessel, T. Noël, Chem. Rev. 2016, 116, 10276-10341. (b) Y. Su, N. J. W. Straathof, V. Hessel, T. Noël, Chem. Eur.
J. 2014, 20, 10562-10589.
[3] For selected work on photoredox catalysis from our group: (a) N. J. W. Straathof, S. E. Cramer, V. Hessel, T. Noël,
Angew. Chem. Int. Ed. 2016, 55, 15549-15553. (b) Y. Deng, X.-J. Wei, H. Wang, Y. Sun, T. Noël, X. Wang, Angew.
Chem. Int. Ed. 2017, 55, 832-836. (c) C. Bottecchia, N. Erdmann, P. M. A. Tijssen, L.-G. Milroy, L. Brunsveld, V.
Hessel, T. Noël, ChemSusChem 2016, 9, 1781-1785. (d) N. J. W. Straathof, B. J. P. Tegelbeckers, V. Hessel, X.
Wang, T. Noël, Chem. Sci. 2014, 5, 4768-4773. (e) N. J. W. Straathof, H. P. L. Gemoets, X. Wang, J. C. Schouten,
V. Hessel, T. Noël, ChemSusChem 2014, 7, 1612-1617. (f) X. Wang, G. D. Cuny, T. Noël, Angew. Chem. Int. Ed.
2013, 52, 7860-7864.
[4] D. Cambie, F. Zhao, V. Hessel, M. G. Debije, T. Noël, Angew. Chem. Int. Ed. 2017, 56, 1050-1054
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Dr. Timothy Noël
Name Timothy Noël
Nationality Belgian
Address Laboratory of Micro Flow Chemistry & Process
Technology, Eindhoven University of Technology, STO
1.37, PO Box 513, 5600 MB Eindhoven, The Netherlands.
E-mail [email protected]
Website www.NoelResearchGroup.com
Professional experience
2012-present Tenured Assistant Professor (Dept. of Chemical Engineering, TU Eindhoven)
• my research group is focused on the combination of reaction engineering,
process technology, organic synthetic chemistry and material science.
2010-2011 Post-doctoral researcher (Massachusetts Institute of Technology, Cambridge,
USA)
• Host: Prof. Dr. Stephen L. Buchwald (Dept. of Chemistry) and collaboration
with Prof. Dr. Klavs F. Jensen (Dept. of Chemical Engineering).
Education
2000-2004 M.Sc. Industrial Chemical Engineer (KaHo Sint Lieven, Ghent, Belgium)
2005-2009 Ph.D. in Organometallic Chemistry (Ghent University, Ghent, Belgium)
• Supervisor: Prof. Dr. Johan van der Eycken
Current Projects
2016 FET Open, NOW, co-applicant (Prof. Hessel Coordinator).
Catalyst Cascade Reactions in ‘One-Flow’ within a Compartmentalized,
Green-Solvent ‘Digital Synthesis Machinery’ – End-to-End Green Process
Design for Pharmaceuticals
3900
k€
2015 VIDI award from Dutch Science Foundation, NWO, personal grant.
Sensitized photoredox catalysis in continuous-flow microreactors
800 k€
2015 Marie Curie Innovative Training Network, coordinator of the project.
Accelerating photoredox catalysis in continuous-flow systems
2,289
k€
2013 ECHO grant from Dutch Science Foundation, NWO.
Breaking the unbreakable: C-H carbonylation in micro flow and vision to
process.
260 k€
Scientific Publications (all are as independent and leading researcher)
101 publications, 14 book chapters, 2 edited books and 1 patent application (To date)
Selected publications
1. A leaf-inspired luminescent solar concentrator for energy efficient continuous-flow
photochemistry. Cambie, D.; Zhao, F.; Hessel, V.; Debije, M.G.; Noël, T. Angew. Chem. Int.
Ed. 2017, 56, 1050-1054 (selected as VIP paper)
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2. Disulfide-Catalyzed Visible-Light Oxidative Cleavage of C=C Bonds and Evidence of an
Olefin-Disulfide Charge-Transfer Complex. Deng, Y.; Wei, X.-J.; Wang, H.; Sun, Y.; Noël,
T.; Wang, X. Angew. Chem. Int. Ed. 2017, 56, 832-836. (selected as Hot paper)
3. Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in
Batch and Flow. Straathof, N. J. W.; Cramer, S. E.; Hessel, V.; Noël, T. Angew. Chem. Int.
Ed. 2016, 55, 15549-15553.
4. Mild and selective base-free C–H arylation of heteroarenes: Experiment and computation.
Gemoets, H. P. L.; Kalvet, I.; Nyuchev, A. V.; Erdmann, N.; Hessel, V.; Schoenebeck, F.;
Noël, T. Chem. Sci., 2017, 8, 1046-1055.
5. Applications of continuous-flow photochemistry in organic synthesis, material science and
water treatment. Cambié, D.; Bottecchia, C.; Straathof, N. J. W.; Hessel, V.; Noël, T., Chem.
Rev., 2016, 116, 10276-10341.
Selected Awards
2016 Thieme Chemistry Journal Award.
2015 VIDI Award (Netherlands Organization for Scientific Research, NWO).
2012 Finalist European Young Chemist Award, EuCheMS Conference.
2011 Incentive Award for Young Researchers (Comité de Gestion du Bulletin des Sociétés
Chimiques Belges).
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Visible light photoredox catalysis with radical anions
I. Ghosh, L. Marzo, R. Shaik, A. Das and B. König*
Faculty of Chemistry and Pharmacy, University of Regensburg, Regensburg, Germany
Visible light photocatalysis has made a huge impact on recent developments in chemical synthesis.
We have explored over the last two years the use of radical anions as photoactive intermediates in
SRN 1 type reactions. An initial photoinduced electron transfer produces a radical anion, which is
colored and stable. This is excited again to a transient doublet state that is strongly reducing.
Transfer of the excess electron to a substrate, e.g. an aryl halide, initiates the aromatic substitution
reaction. Our initial system based on perylenediimide1 suffered from low solubility of the
photocatalyst and was improved by using the well-established organic dye rhodamine 6G.2
The reaction principle was established for C-C cross coupling reactions,3 the synthesis of annulated
heteroarenes4 and the synthesis of phosphonates.5
Recently, we were able to improve the performance of the reaction further by introducing a
sensitization-induced electron transfer instead of direct excitation of the redox active photo-
catalysts. This new principle generates highly reactive synthesis intermediates with unprecedented
ease from green and blue light.
References
1) I. Ghosh, T. Ghosh, J. I. Bardagi, B. König, Science 2014, 346, 725.
2) I. Ghosh, B. König, Angew. Chem. Int. Ed. 2016, 55, 7676.
3) a) L. Marzo, I. Ghosh, F. Esteban, B. König, ACS Catal. 2016, 6, 6780. B) I. Ghosh, L. Marzo, A. Das, R.
Shaikh, B. König, Acc. Chem. Res. 2016, 49, 1566.
4) A. Das, I. Ghosh, B. König, Chem. Commun. 2016, 52, 8695.
5) R. S. Shaikh, S. J. S. Düsel, B. König, ACS Catal. 2016, 6, 8410.
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Burkhard König Institut für Organische Chemie Einhausen 38b Universität Regensburg D-93138 Lappersdorf Universitätsstr. 31 Germany D-93040 Regensburg, Germany phone: +49-941-8703153 phone: +49-941-943-4576/5 mobile: +49-15201678001 fax: +49-941-943-1717 e-mail: [email protected]
Curriculum Vitae
Personal data Date of Birth 23/6/1963 Nationality German martial status married, one child Education University education in Chemistry 6/96 venia legendi, Habilitation (organic chemistry), Technical University
of Braunschweig, Germany 9/91 Ph.D. (Dr. rer. nat) (summa cum laude), University of Hamburg,
Germany 9/88 M.S. (Hauptdiplom) (magna cum laude, 1.0), University of Hamburg,
Germany 11/85 B.S. (Vordiplom) (magna cum laude, 1.3), University of Hamburg,
Germany Experience 10/99 - present Full professor at the Department of Chemisty, University of
Regensburg, Germany. Research areas: Physical-organic chemistry; supramolecular chemistry, photocatalysis, catalytic conversion of renewable resources.
6/93 – 9/99 Research group leader at the Department of Chemistry, Technical University of Braunschweig, Germany.
1/92 - 5/93 Postdoctoral fellow with Prof. Dr. B. M. Trost at Stanford University, U.S.A.
10/91 - 1/92 Visiting research fellow with Prof. Dr. M. A. Bennett at the Research School of Chemistry, Australian National University, Canberra, Australia
3/88 - 9/91 Graduate research with Prof. Dr. A. de Meijere at the University of Hamburg
Awards and activities
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• Editorial board member of “Chemistry – A European Journal” and “European Journal of Organic Chemistry (Chair) (since 2014)
• UN-Decade Award on Sustainability 2011/2012
• Dean of the faculty of chemistry since 10/2011
• Literature award of the Fonds of the German Chemical Industry 2007
• Chairman of the Liebig Vereinigung (National organic devision; 2008 – 2012)
• Member of the excecutive board of the German Chemical Society (2004 - 2007)
• Chairman of the „Arbeitsgemeinschaft Deutscher Universitätsprofessoren Chemie (ADUC)
• (2005-2007)
• Member of the International Advisory Board of the Institute for Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Prag (since 2004)
• Member of the International Advisory Board of the “European Journal of Organic Chemistry” (since 2004)
• Invitation fellowship award of the `Japan Society for the Promotion of Science´ (1996)
• Award of the Dr. Otto Röhm Gedächnisstiftung (1995)
• Fellowship of the Deutsche Forschungsgemeinschaft (Habilitationsstipendium)
• Fellowship of the Fonds der Chemischen Industrie (Liebig-Stipendium)
• Postdoctoral fellow of the Alexander von Humboldt foundation (Feodor-Lynen fellow)
• Graduate fellow of the Studienstiftung des Deutschen Volkes
Publication record Scientific papers and reviews: 314 / H-index 45 books, book reviews, science related articles: 60
Regensburg 11/2016 For additional information, please visit: http://www-oc.chemie.uni-regensburg.de/koenig/index.html
Ten self selected papers
1. Eosin Y Catalyzed Visible Light Oxidative C-C and C-P bond Formation (Times Cited: 238)
D. P. Hari, B. Koenig* Org. Lett. 2011, 13, 3852 – 3855. DOI: 10.1021/ol201376v
The paper disclosed the first example of using the organic dye eosin Y as visible light photocatalyst;
the compound is now widely used by researchers to replace precious Ru(bipy)3Cl2 in synthesis.
2. Metal free, Visible Light Mediated Direct C-H Arylation of Heteroarenes with Aryl Diazonium salts
(Times Cited: 200)
D. P. Hari, P. Schroll, B. König* J. Am. Chem. Soc. 2012, 134, 2958 – 2961. DOI: 10.1021/ja212099r
The Meerwein arylation reaction is known since more than 100 years, but the original protocol using
copper salts gives only moderate yields. This has limited the use of the reaction in synthesis. We
describe here for the first time the activation of diazonium salts by visible light photoredox catalysis
providing a much cleaner reaction and good to excellent product yields. The “Photo Meerwein”
reaction has since then been widely applied in organic synthesis.
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3. The Photocatalyzed Meerwein Arylation: Classic Reaction of Aryl Diazonium Salts in a New Light
(Times cited: 204)
D. P. Hari, B. König* Angew. Chem. Int. Ed. 2013, 52, 4734 – 4743. DOI: 10.1002/anie.201210276
We have summarized the rapid expanding synthetic applications of our „Photo Meerwein“ arylation
reaction in this review.
4. Visible Light Photocatalytic Synthesis of Benzothiophenes (Times Cited: 85)
D. P. Hari, T. Hering, B. König* Org. Lett. 2012, 14, 5334 – 5337. DOI: 10.1021/ol302517n
Application of the „Photo Meerwein“ reaction in the synthesis of important heterocycles.
5. Visible light Promoted Stereoselective Alkylation by Combining Heterogeneous Photocatalysis with
Organocatalysis (Times Cited: 85)
M. Cherevatskaya, M. Neumann, S. Füldner, C. Harlander, S. Kümmel, S. Dankesreiter, A. Pfitzner,
K. Zeitler, B. König* Angew. Chem. Int. Ed. 2012, 51, 4062 – 4066. DOI: 10.1002/anie.201108721
This is the first report combining stereoselective organocatalysis with heterogeneous semiconductor
photocatalysis replacing homogeneous photocatalysts, like Ru or Ir complexes by robust and available
semiconductors.
6. Reduction of aryl halides by consecutive visible light-induced electron transfer processes (Times Cited:
33)
I. Ghosh, T. Ghosh, J. I. Bardagi, B. König* Science 2014, 346, 725-728.
This is the first report on consecutive photoinduced electron transfer in visible light photocatalysis.
7. Molecular Imprinting of Luminescent Vesicles (Times Cited: 21)
S. Banerjee, B. König* J. Am. Chem. Soc. 2013, 135, 2967 – 2970. DOI: 10.1021/ja4001568
First report of molecular imprinting on the surface of a fluid vesicle giving luminescent nanosensors.
8. Regulation of Human Carbonic Anhydrase I (hCAI) Activity by Using a Photochromic Inhibitor (Times
Cited: 50)
D. Vomasta, C. Högner, N. R. Branda,* B. König* Angew. Chem. Int. Ed. 2008, 47, 7644 - 7647.
DOI: 10.1002/anie.200802242
Photochromic enzyme inhibitor based on a dithienylethene chromophore allows the reversible light
controlled inhibition of an enzyme.
9. Potent and selective inhibitors of breast cancer resistance protein (ABCG2) derived from the p-
glycoprotein (ABCB1) modulator tariquidar (Times Cited: 62)
M. Kühnle, M. Egger, C. Müller, A. Mahringer, G. Bernhardt, G. Fricker, B. König,* A. Buschauer*
J. Med. Chem. 2009, 52, 1190 – 1197. DOI: 10.1021/jm8013822
The compound with currently highest potency and selectivity for ABCG2 inhibition is reported.
10. Conversion of carbohydrates into 5-hydroxymethylfurfural in highly concentrated low melting mixtures
(Times Cited: 91)
F. Ilgen, D. Ott, D. Kralisch, C. Reil, A. Palmberger, B. König* Green Chem. 2009, 11, 1948 – 1954.
DOI: 10.1039/b917548m First report of the efficient and solvent-free conversion of carbohydrates into
HMF using a low melting mixture.
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New photoredox-induced cascade reactions
Malte Brasholza,*
aUniversity of Hamburg, Department of Chemistry – Institute of Organic Chemistry, Hamburg, Germany
Photoredox-mediated one-electron reduction of organic halides is a mild and efficient method to
generate the corresponding carbon-centered radicals. While the reduction of activated acyl halides
can readily be accomplished using common ruthenium(II) polypyridyl photocatalysts, unactivated
alkyl, alkenyl and aryl halides require more strongly reducing conditions, and in particular
iridium(III) polyheteroaryl complexes possess suitable redox potentials to bring about these more
challenging reductive transformations.1
Photoinduced free radical additions have been utilized extensively in the synthesis of
functionalized heterocycles, however, mostly giving aromatic products. We developed
dearomative radical additions onto indoles, and an iridium(III)-catalyzed reductive radical (4+2)-
cyclization between N-iodoethylindoles and alkenes led to valuable tricyclic benzindolizidine
products.2 Further extension of our methodology enabled a new stereoselective synthesis of
functionalized hexahydrocarbazoles, based on an unprecedented dearomative radical (4+2)-
cyclization/1,4-addition cascade between 3-(2-iodoethyl)indoles and acceptor-substituted alkenes.
The photoredox-induced cascade reaction simultaneously generated three C-C and one C-H bonds,
along with three contiguous stereogenic centers.3
Mechanistic aspects of these dearomative radical cyclizations of indole derivatives will be
discussed, as well as synthetic applications of the heterocyclic products, which are highly valuable
intermediates for the synthesis of novel antibiotics as well as unnatural ring homologs of polycyclic
indoline alkaloids.
References
[1] Reviews: (a) C. K. Prier, D. A. Rankic, D. W. C. Mac Millan, Chem. Rev. 2013, 113, 5322-5363.
(b) D. Ravelli, S. Protti, M. Fagnoni, Chem. Rev. 2016, 116, 9850-9913.
[2] S. Mühmel, D. Alpers, F. Hoffmann, M. Brasholz, Chem. Eur. J. 2015, 21, 12308-12312.
dearomative radical (4+2)-cyclization (4+2)-cyclization / 1,4-addition cascade
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[3] D. Alpers, M. Gallhof, J. Witt, F. Hoffmann, M. Brasholz, Angew. Chem. 2017, 129, 1423-1427; Angew. Chem.
Int. Ed. 2017, 56, 1402-1406.
Malte Brasholz studied Chemistry at Freie Universität Berlin and obtained his PhD from the
same institution in 2007, under the guidance of Prof. Hans-Ulrich Reissig. A short-term stay in
the laboratory of Prof. Hisashi Yamamoto at the University of Chicago in 2008 was followed by
one year of postdoctoral research in the group of Prof. Steven V. Ley at the University of
Cambridge. A second year of postdoctoral studies led Malte to Australia, where he worked at
CSIRO Molecular and Health Technologies in association with Prof. Andrew B. Holmes at the
University of Melbourne. In 2010, he was appointed Research Scientist at CSIRO Materials
Science and Engineering. From April 2012, Malte established an independent research group at
the Institute of Chemistry at the University of Hamburg.
Academic CV
.
2012 Assistant Professor of Organic Chemistry, University of Hamburg
2010 Research Scientist, CSIRO Materials Science and Engineering, Melbourne
2009 Postdoctoral fellow, CSIRO Molecular and Health Technologies
and group of Prof. Andrew B. Holmes, University of Melbourne
2008 Postdoctoral fellow, group of Prof. Steven V. Ley, University of Cambridge
2007 Short-term scholar, group of Prof. Hisashi Yamamoto, University of Chicago
2007 PhD in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin
2004 Diplom degree in Chemistry, group of Prof. Hans-Ulrich Reissig, Freie Universität Berlin
Awards and Fellowships:
.
2016 GIAN lectureship, Government of India
2015 Donation by Dr. Otto Röhm Gedächtnisstiftung
2014 Thieme Journal Award
2009 Postdoctoral fellowship, CSIRO Office of the CEO Awards Scheme
2008 Postdoctoral fellowship, Deutsche Forschungsgemeinschaft (DFG)
2005 PhD fellowship, Fonds der Chemischen Industrie (FCI)
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Photoinduced Electron Transfer in Base-promoted Homolytic Aromatic
Substitution and Related Systems. Is t-butoxide anion a key ingredient?
M. E. Budén;a J. F. Guastavino,a J. I. Bardagí, a Marcelo Puiatti a and R. A. Rossia*
a Instituto de Investigaciones en Físicoquímica de Córdoba, INFIQC, Córdoba, Argentina
In the recent years, there is a booming of research in transition metal-free couplings of ArX to
arenes to form biaryls (eq 1). These reactions are triggered by alkali metal tert-butoxides in the
presence of various additives via Base-promoted Homolytic Aromatic Substitution (BHAS).1,2 In
2008, the original report presented by Itami showed that KOtBu promoted the arylation of pyrazine
and other electron‐poor arenes from ArI or ArBr, under elevated temperatures or MW irradiation.3
Later, different research groups have reported the construction of biaryls and stilbene derivatives
from unactivated aromatic compounds by direct C-H activation of benzene or styrene using
NaOtBu or KOtBu in the presence of a range of organic additives as ligands.2 As a consequence,
the role of these organic additives in radical initiation attracted much research interest and different
mechanisms have been proposed.4
Previously we reported on photoredox reactions for synthesis of biaryls (BHAS) and styrenes
(Mizoroki−Heck-type) as a new alternative to induce these transformations at room temperature
(eqs 1 and 2).5 Now, we propose a new alternative to induce these photoreactions, that involves
dimsyl anion as a key ingredient. However, C-H functionalization of alkenes is produce without
any solvent. Computational studies were performed to help to understand the initiation steps of
these processes.
1. Studer, A.; Curran, D. P. Angew. Chemie Int. Ed. 2011, 50, 5018–5022.
2. a) Sun, C.; Shi, Z. Chem. Rev. 2014, 114, 9219–9280. b) Hussain, I.; Singh, T. Adv. Synth. Catal. 2014, 356, 1661–
1696. c) Mehta, V. P.; Punji, B. RSC Adv. 2013, 3, 11957 and references cited herein.
3. Yanagisawa, S.; Ueda, K.; Taniguchi, T.; Itami, K. Org. Lett. 2008, 10, 4673–4676.
4. a) Zhou, S.; Anderson, G. M.; Mondal, B.; Doni, E.; Ironmonger, V.; Kranz, M.; Tuttle, T.; Murphy, J. A. Chem.
Sci. 2014, 5, 476–482. b) Zhou, S.; Doni, E.; Anderson, G. M.; Kane, R. G.; MacDougall, S. W.; Ironmonger, V. M.;
Tuttle, T.; Murphy, J. A. J. Am. Chem. Soc. 2014, 136, 17818–17826. c) Patil, M. J. Org. Chem. 2016, 81, 632–639.
5. a) Budén, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett. 2013, 15, 1174–1177. b) Guastavino, J. F.; Budén, M.
E.; Rossi, R. A. J. Org. Chem. 2014, 79, 9104–9111.
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María Eugenia Budén
Address Ernesto La Padula 865. (CP 5000), Cordoba, Argentine
Telephone (+54) 0351 460 2736
Nationality Argentine
Date of birth
13th of August 1981
CURRENT RESEARCH POSITION
From April 2013
Assistant researcher at CONICET. Title: Photoinduced Direct C-H-Arylation via Base-Promoted
Homolytic Aromatic Substitution
FELLOWSHIP AWARDS
From April 2010 to March 2012
Postdoctoral Research Fellowship from the National Research Council of Argentina.
Title: Synthesis of Biaryls and Heterocycles by Metal-Catalyzed Organic Reactions and SRN1.
Research Advisor: Dr. Roberto A. Rossi and Sandra E. Martin
From April 2005 to March 2010
Doctoral Research Fellowship from the National Research Council of Argentina. Thesis Title: New
Tandem Reactions by SRN1 Mechanisms. Research Advisor: Dr. Roberto A. Rossi.
RESEARCH INTERESTS
Organic synthesis and photochemistry – Radical chemistry – Redox processes in organic syntheses –
Heterocyclic chemistry-.
SCIENTIFIC PUBLICATIONS
13 papers, 5 chapter of books and 22 oral and poster presentations.
STAYS IN INTERNATIONALLY RECOGNIZED CENTRES
From April 2011 to October 2011
Laboratori de Química Farmacèutica (Unitat Associada al CSIC), Facultat de Farmàcia, Universitat
de Barcelona, Barcelona, Spain.
Topic: Tetrasubstituted alkenes by metathesis of 1,1-disubstituted alkenes: potential application for
the synthesis of belt compounds
Research Advisor: Dr. Pelayo Camps
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KOtBu promoted intermolecular cross-coupling through electron transfer
A. Tlili,a,* J. Bergèsb and M. Tailleferb,*
aICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Villeurbanne, France bENSCM - UMR 5253 - Institut Charles Gerhardt, Montpellier, France (Times New Roman, italicized in 10 pt.)
The talk will mainly focus on our recent ongoing research program based on transition metal free
cross-coupling reactions. Indeed, we recently developed a Matsuda-Heck coupling reaction
allowing the formation of stilbenes derivatives using arenediazonium salts and styrene derivatives
as coupling partners. Theses reactions proceed under transition metal and irradiation-free
conditions.1
1.J. Bergès, A. Tlili, M. Taillefer, manuscript in preparation
R
N2+BF4
-
+R
KOtBuR'
R'
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Anis TLILI [email protected] ICBMS-SURCOOF + 33 4 72 44 85 28 Université Claude Bernard - Lyon 1
43 Bd du 11 novembre 1918
Bat. Raulin (4ème étage)
69622 Villeurbanne Cedex – France
Date of birth: February 25, 1983, Married
CNRS Research Fellow
Experience
10/2014- CNRS Research Fellow
To date ICBMS - SURCOOF (UMR CNRS 5246 - Lyon), Université Claude Bernard - Lyon 1.
09/2013- Chercheur postdoctoral, CEA - Commissariat à l'énergie atomique -Saclay, France.
08/2014 Synthesis of new phosphine based frustrated Lewis pair for the reduction of CO2.
In collaboration with the group of: Dr. A. Marinetti
01/2012- Chercheur postdoctoral, Leibniz-Institut für Katalyse, Allemagne, Prof. M. Beller.
08/2013 Transition metals catalyzed reactions under carbon monoxide.
2011 Internship (2 months), ENS Paris, France, Supervised by Dr. A. Jutand.
Electrochemical studies on Cu-catalyzed C-N and C-O Bond formating reactions
2008-2011 Thèse en chimie, ENSC Montpellier, France, Dr. M. Taillefer.
Cu -catalyzed C-C, C-N and C-O Bond formating reactions.
2007-2008 Master internship (6 mois), Université de Bourgogne, Dijon, France, Prof. S.
Jugé.
New P-Chirogenic diphosphine complexes.
PUBLICATIONS AND PATENTS
33 publications & patents
2 book chapters
Awards
First Price IDEAS COMPETITION “CATALYSIS 2020“, Leibniz-Institut für Katalyse
Awarded Leibniz grant for Post-doctoral researcher (01/2012-08/2013), Leibniz-Institut für
Katalyse
Solvias AG lecture 2016
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“The Palme d’Or goes to …”. A search for the best functional for dealing with
anionic organic species
M. Puiatti;a,* J. L. Borioni;b D. M. A. Vera b and A. B. Pierinia,
aINFIQC- Instituto de Investigaciones en Físicoquímica de Córdoba, Córdoba, Argentina b Dpto. Química, Fac. Cs. Exactas y Naturales, Universidad Nacional de Mar del Plata, Mar del Plata, Argentina
During the last few decades, density functional theory (DFT) has become the method of choice
in quantum chemical studies. Indeed, many experimental investigations routinely include such
calculations, using a popular code, a standard basis, and a standard functional approximation.1 It is
well known that DFT has provided approximations that work quite well for some problems and fail
for others.2 Hence, a proper recommendation should be to search for the DFT functional that works
better within the problem to be studied. In the present study we addressed the overall performance
of 23 different DFT functionals and ab initio methods for studying anionic organic species.
In order to evaluate its scope and limitations, electron affinities (EA) and reduction potentials
(𝐸𝑅𝑒𝑑0 ) were computed. A set of 60 molecules was employed for the calculation of EAs, in the range
of 0 to -3.4 eV. Besides, 62 compounds were selected for the computation of the 𝐸𝑅𝑒𝑑0 , with
potentials, measured in acetonitrile, from -2.71 V to 0.06 V (vs. standard hydrogen electrode, SHE).
For compounds with negative EAs, hybrid GGA gave better results than pure and meta GGA double
hybrid functionals and ab initio methods yield poorly with MADs higher than 0.5 eV.
The calculations of 𝐸𝑅𝑒𝑑0 are strongly dependent on the quality of the solvation energies of the
charged species. This was evidenced in the correlation of calculated absolute 𝐸𝑅𝑒𝑑0 vs. experimental
𝐸𝑅𝑒𝑑0 . However, there is a significant improvement after the use of a proper redox partner. The best
results were obtained with hybrid GGA functionals, B3PW91 and PBE0. TPSSh and M06 were
the better meta GGA. Pure GGA functionals gave good results, with low dispersion, but high
MADs, that could improve by choosing a proper reference.
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The ideal scenario should give a podium with some functionals that outperform the others.
However, there is a suitable DFT functional for each problem instead of a universal one that could
solve almost all the situations within different conditions.
References:
1- Burke, K., J Chem Phys, 2012, 136, 150901.
2- Medvedev, M. G.; Bushmarinov, I. S.; Sun, J.; Perdew, J. P.; Lyssenko, K. A. Science, 2017, 355, 49-52.
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MARCELO PUIATTI
Nationality: Argentine
Date of Birth: 10th of February 1977
Address: Arq. Ernesto La Padula 865. Ba: Parque Vélez Sarsfield. Córdoba. Argentina.
Telephone: +54-351-156742579
Email: [email protected]
CURRENT POSITION
From 2004
From 2009
Assistant Profesor. Facultad de Ciencias Químicas. Universidad Nacional de Córdoba.
Researcher. INFIQC. CONICET. “Application of Molecular Modeling to the Study of Organic and Bio-organic Systems”. Former Director: Prof. Dra. Adriana B. Pierini
RESEARCH INTEREST
Electron Transfer Reactions; Radical Anions; DFT; Photochemistry; AChE Inhibitors; Molecular Modeling
SCIENTIFIC PUBLICATIONS
11 Scientific Articles, 25 Presentations to Workshops and Scientific Meetings, 3 Invited Conferences.
MOST RELEVANT ARTICLES
“In search of the best DFT functional for dealing with organic anionic species”. José L. Borioni, Marcelo Puiatti, D. Mariano A. Vera and Adriana B. Pierini. Phys. Chem. Chem. Phys. Accepted. doi: 10.1039/C6CP06163J. “In search for an optimal methodology to calculate the valence electron affinities of temporary anions.” Puiatti, M.; Vera, D.M.A; Pierini, A. B.. Phys. Chem. Chem. Phys., 2009, 11, 9013 - 9024. “Species with negative electron affinity and standard DFT methods. Finding the valence anions” Marcelo Puiatti, D. Mariano A. Vera, Adriana B. Pierini. Phys. Chem. Chem. Phys., 2008, 10,1374-1379.
FORMATION
2006. PhD. Doctor en Ciencias Químicas. “Study of Electron Transfer Oxidation Reactions”. Advisor: Dra. Alicia B. PEÑÉÑORY. Fac. de Cs. Químicas. Universidad Nacional de Córdoba.
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2006-2009 Post-doctoral Position. “Computational Chemistry Applied to Study of Intermediate Species of Electron Transfer Reactions”. Director: Dra. Adriana B. Pierini. Fac. Ciencias Químicas. Universidad Nacional de Córdoba. Post-doctoral Fellowship CONICET.
2011-2012 Post-doctoral Position. Life Sciencies Department BSC Barcelona. “Electronic and Atomic Protein Modeling”. Director: Dr. Víctor Guallar. 01/02/2011 hasta 28/02/2012. MAE Fellowship Spain.
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Characterization of single electron transfer steps in water oxidation through
DFT calculations
Feliu Maseras
a Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science of Technology, Av. Països Catalans 16,
43007 Tarragona, Catalonia, Spain (Times New Roman, italicized in 10 pt.) bDepartament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain
Computational homogeneous catalysis has been traditionally dominated by two-electron transfer
processes.1 The increasing interest in the catalytic processes involving first row transtion metals
has lead to the identification of a number of processes where single electron transfer processes play
a critical role.2-6 In this presentation we will discuss some of our recent contributions in the field,
with a special focus on copper-catalyzed O-O water oxidation3,6 (see Figure). Calculations
demonstrate that single electron transfer processes replace in some cases the two-electron transfer
water nucleophilic attack mechanism, the main operating mode for second- and third-row transition
metals.
References (Times New Roman, 10 pt.), denoted by superscript numbers in the text, it should be listed at the end of
the text using ACS format. 1. Sameera, W. M. C.; Maseras, F. WIREs Comp. Mol. Sci. 2012, 2, 375-385. 2. Jover, J.; Spuhler, P.; Zhao, L. G.; McArdle, C. Catal. Sci. Tech. 2014, 4, 4200- 4209. 3. Garrido-Barros, P.; Funes-Ardoiz, I.; Drouet, S.; Benet-Buchholz, J.; Maseras, F.; Llobet, A. J. Am. Chem. Soc.
2015, 137, 6758-6761. 4. Fernandez-Alvarez, V. M.; Nappi, M.; Melchiorre, P.; Maseras, F. Org. Lett. 2015, 17, 2676-26795. 5. Funes-Ardoiz, I.; Maseras, F. Angew. Chem. Int. Ed. 2016, 55, 2764-2767. 6. Funes-Ardoiz, I.; Garrido-Barros, P.; Llobet, A.; Maseras, F. ACS Catal. 2017, DOI:10.1021/acscatal.6b03253
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Feliu Maseras
Contact information
Experience
Research group leader in Institute of Chemical Research of Catalonia (ICIQ) since 2004
Assoc Prof in Universitat Autònoma de Barcelona since 1998
Assoc Researcher in Montpellier 1996-98
Post-doctoral researcher in Okazaki 1992-94
Education
PhD in Chemistry, Universitat Autònoma de Barcelona, 1991
Research topics
Research interest focused in the design an application of QM/MM methods to problems of
practical interest and the computational study of the reactivity of molecular systems containing
transition metal atoms.
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Charge Transfer Processes : Prime Role of Optimized Molecular Orbitals
V. Roberta,*, A. Domingoa, T. Kraha and B. Meyera
aLaboratoire de Chimie Quantique, CNRS Université de Strasbourg, Strasbourg, France
abstract : The key role played by the molecular orbitals in describing electron transfer processes
is examined in mixed-valence compounds (see Figure, Fe3+/Fe2+ biomimetic non-heme1) and
analogues. It is suggested that the extent of
electronic reorganization induced by
intervalence charge transfer can reach up to
several electron-volts2,3. By means of ab initio
calculations (wave-function type,
CASSCF/CASPT2), it is shown that the
energetic profile shows strong similarities to the
Marcus’s theory. Such observation questions
the standard quantum chemistry approaches
used to describe internal electron transfer
phenomena in molecular science devices.
References: 1. Balasubramanian, R.; Blondin, G.; Canales, J. C.; Costentin, C.; Latour, J.-M.; Robert, M.; Savéant, J.-M. J Am.
Chem. Soc. 2012, 134, 1906. 2. Domingo, A.; Angeli, C.; de Graaf, C.; Robert, V. J. Comp. Chem. 2015, 36, 861. 3. Meyer, B. Domingo, A.; Krah, T.; Robert, V. Dalton. Trans. 2014, 43, 11209.
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Vincent ROBERT Date of birth: March 17th 1969
E-mail: [email protected] - webpage: http://quantique.u-strasbg.fr/pperso/vincent/
CURRENT POSITION
Full Professor Strasbourg University, Laboratoire de Chimie Quantique
Director of Laboratoire de Chimie Quantique, Strasbourg
Director of Réseau Chimie Théorique Français Grand-Est
Member of LabEx Complex Systems, Strasbourg University
Coordination Leader ANR French Research Project (2007-2010)
Supervisor 1 PhD, 1 PostDoc
SCIENTIFIC BACKGROUND 2010-present Full Professor (section 31), Strasbourg University
1997-2010 Assistant Professeur, Physical Chemistry, Lyon 1 University
2001-2003 Sabbatical CNRS, Laboratoire de Chimie et Physique Quantiques,
Toulouse
SCIENTIFIC ACTIVITIES semi empirical calculations, ab initio, methodology - spectroscopies, magnetic systems,
macroscopic properties, spintronics
Publication (98) 62 ACS, APS Journals and 36 in Eur. Journals
2 reviews, 2 book chapters, 3 cover pages
Invited Professor Nagoya University, Japan, September 2007, 2009, 2012
Tarragona University, Spain, April-May 2008
Conferences 20 invited conferences, 30 invited seminars
5 Reference Publications
1. Mizumo, A.; Shuku, Y.; Suizu, R.; Matsushita, M.; Tsuchiizu, M.; Reta Maneru, D.; Illas,
F.; Robert, V.; Awaga, K. J. Am. Chem. Soc. 2015, 137, 7612
2. Domingo, A.; de Graaf, C.; Angeli, C.; Robert, V. J. Comp. Chem. 2015, 36, 861
3. Krah, T.; Ben Amor, N.; Maynau, D.; Berger, J.A.; Robert, V. J. Mol. Mod. 2014, 20, 2240
4. Vérot, M.; Borshch, S.A.; Robert, V. J. Chem. Phys. 2013, 138, 094105
5. Perraud, O.; Robert, V.; Gornitzka, H.; Martinez, A.; Dutasta, J.P. Angew. Chem. Int. Ed.
2012, 51, 504
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Exploring the reactivity of the Kagan’s reagent from a theoretical perspective
L. Perrin;a,* X. Zhaob and L. Maronb
aUniversité Lyon 1, CNRS, INSA, CPE, UMR 5246, ICBMS, ITEMM, 43 Bd du 11 novembre 1918, 69622
Villeurbanne cedex, France b LPCNO, Université de Toulouse, INSA, UPS, CNRS, 135 avenue de Rangueil, F-31077 Toulouse, France
The Kagan’s reagent (SmI2) is one of the most versatile single-electron reducing agent in organic
synthesis. Since its seminal report,1 the scope off application of this reagent has been largely
enriched by adjusting the reaction conditions and especially the proper solvent / co-solvent(s)
combinations.2 Modeling single electron transfer mediated by f-element proved to be inaccessible
until recently.3 This contribution details the modeling strategy developed for the modeling of the
reactivity SmI2 in complex environments and addresses how co-solvents such as HMPA, water and
amine not only modify the reducing power of SmI2 but also strongly affect reaction mechanisms.
More precisely, our pioneering mechanistic investigation addresses the mechanism by which alkyl-
halides and various carbonyl derivatives are selectively reduced by SmI2 depending on the reaction
conditions.4 A particular emphasis will be laid on the role played by bimetallic intermediates and
subsequent Bimetallic Proton Coupled Electron Transfer (BPCET).
FIG. Bimetallic reduction of aliphatic esters by SmI2 in ternary THF/water/amine
Namy, J. L.; Girard, P.; Kagan, H. B. Nouv. J. Chim. 1977, 1, 5; Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem.
Soc. 1980, 102, 2693.
Procter, D. J.; Flowers, R. A., II; Skrydstrup, T. Organic Synthesis Using Samarium Diiodide: A Practical Guide;
RSC Publishing: Cambridge, 2010; Szostak, M.; Procter, D. J. Angew. Chem., Int. Ed. 2011, 50, 7737. Szostak, M.;
Spain, M.; Procter, D. J. Chem. Soc. Rev. 2013, 42, 9155.
Kefalidis, C. E.; Essafi, S.; Perrin, L.; Maron, L. Inorg. Chem. 2014, 53, 3427.
Kefalidis, C. E.; Perrin, L.; Maron, L. Eur. J. Inorg. Chem. 2013, 22-23, 4041 and unpublished results.
Lionel Perrin received his Ph.D. in 2004 from Université Montpellier (Odile Eisenstein and Laurent Maron directors) and joined the CNRS in 2005. Since 2013, he is group leader of Interface Theory Experiment: Mechanism and Modeling (ITEMM) at Université Lyon 1, he focuses on the interplay between experiments and theory for polymerization and multistep organic reactions catalyzed by organometallic species.
Curriculum 2016 « Habilitation à Diriger des Recherches » Université Lyon 12004-2005 CNRS Post-doctoral fellow, CEA-Saclay2001-2004 PhD of Theoretical Physiocal-Chemistry Université Montpellier II
2000-2001 Master of Theoretical Physiocal-Chemistry Université Toulouse III1997-2000 Ingénieur Chimiste Ecole Supérieure de Chimie Organique et Minérale ESCOM
Lab Experiences2013- Chargé de recherche au CNRS (UMR 5246, ICBMS), Univ-Lyon 1
ITEMM Group leader Theoretical/experiment interface, molecular modeling and reaction mechanism exploration. Folding and self-assembly mechanism.
2008-2013 Chargé de recherche au CNRS (UMR 5215, LPCNO), INSA-Toulouse Computational chemistry applied to organometallic and bio-inorganic chemistry
2005-2008 Chargé de recherche au CNRS (URA 2096, PMTE), CEA-Saclay Modeling of the dynamics and reactivities of metalloproteins
2004-2005 Post-doctoral fellow at CEA-Saclay, F. André et M. Delaforge (CNRS valorisation / Servier)Computational investigation of recognition mechanism of P450s
2001-2004 Thèse de doctorat à l’Université Montpellier II, O.Eisenstein et L.Maron (Michelin, CIFRE) Theoretical investigation of the structure and reactivity of organolanthanide complexes
Major CollaboratorsR.A. Andersen UC-Berkeley, USAI. Marek Technion Haifa, IsraëlD.J. Procter University of Manchester, UK S. Maeda Hokkaido University, JaponK. Morokuma FIFC-Kyoto, Japon
C. Boisson CPE-LyonM. Taoufik CPE-LyonC. Taillefumier Université Clermond-FerrandO. Eisenstein Université Montpellier IIManufacture MICHELIN
Recent publicationsDeciphering selectivity in organic reactions: A multifaceted problem. Balcells D, Clot E, Eisenstein O, Nova A, Perrin L: Acc. Chem. Res. 49:1070-1078, 2016Spécial Issue on Computational Catalysis for Organic Synthesis Preparation and Reactivity of Acyclic Chiral Allylzinc Species via a Zn-Brook Rearrangement. Leibeling M, Shurrush KA, Perrin L, Marek I: Angew. Chem. Int. Ed. 55:6057-6061, 2016Weak backbone CH…O=C and side chain tBu…tBu London interactions help promote helix folding of achiral NtBu peptoids. Angelici G, Bhattacharjee N, Roy O, Faure S, Didierjean C, Jolibois F, Perrin L*, Taillefumier: Chem. Commun. 52:4573-4576, 2016New perspectives in organolanthanide chemistry from redox to bond metathesis: Insights from theory. Kefalidis CE, Castro L, Perrin L, Del Rosal I, Maron L: Chem. Soc. Rev. 45:2516-2543, 2016. Ethylene-Butadiene Copolymerization by Neodymocene complexes: a Ligand Structure / Activity / Polymer Microstructure Relationship based on DFT calculations. Nsiri H, Belaid I, Larini P, Thuilliez J, Boisson C, Perrin L*: ACS Catal. 6:1028-1036, 2016.