boss 12 conference report siti aishah hasbullah
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Conference report BOSS12 Siti Aishah HasbullahTRANSCRIPT
CONFERENCE REPORTBOSS 12
Siti Aishah Hasbullah
20th October 2010
Prof. Eric JACOBSEN(HARVARD UNIVERSITY, Cambridge, United
States)
Prof. David MACMILLAN(PRINCETON UNIVERSITY, Princeton, United
States)
Tetrahedron Lecture
Prof. David MacMillan
Princeton University
Tetrahedron Lecture 1: The Advent and Growth of Organocatalysis and Iminium Catalysis
The Roots of Organocatalysis: 19th Century Reaction Discovery
H
OHCN
O
OHWohler, F.; Liebig, J. Annal. Pharm. 1832, 3,249
H CN
HO CN OH
Basic for carbene catalysis
O
Me
O
Me
HO
O
OHO
3 mol% cat
DMFNH
CO2H
Cat. (S)-proline
The Early Use of Organic Catalysis in Enantioselective Synthesis: Hajos-Parrish
-Intramolecular Aldol: Hajos-Parrish, JOC, 1974,39,1615
-Extraordinary result that was well received by the chemical synthesis community
- Betweeen 1960 – 2001, no review articles on the collective use of organocatalyst.
Enantioselective Catalysis using Small Organic Molecules: Epoxidation
O10 mol% cat
Oxone
50 - 98% ee
O
OO
O
O
O
OO
OO
O
N
OF
Yang CatalystJACS, 1996, 118, 491
Shi catalystJACS, 1996, 118,9806
Denmark CatalystJOC,1998, 63, 2810
-Employed ketones as enantioselectives catalysts
-Demonstrated that organic catalyst could be employed to solve major chemical problems
-Involved the invention of a single catalyst for a single reaction type
MacMillan: The Advent of Iminium Catalysis and the Field of Organocatalysis
New Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels-Alder
Reaction
MacMillan: The Advent of Iminium Catalysis and the Field of
Organocatalysis..Cont…..
This manuscript conceptualized the field of organocatalysis for the first time in 3 important ways:
1. Outlined the potential benefits of using organic molecules as asymmetric catalysts for industry or academia based on cost, availability and ease to use
2. Introduced the concept of generic mode of activation for organic catalysis that could be used over many reaction types
3. Introduced for the first time, the terminology organocatalysis, organic catalysis and organocatalytic
Tetrahedron Lecture 2: Enamine Catalysis: Teaching and Old Dog Some Tricks
Enamine Catalysis : Early Adoption in Catalysis
- Woodward-Wieland-Miescher enamine cyclization for steroid synthesis
O
Me H
MeOH
OHH5IO6
O
Me H
MeO
O
O
Me H
Me
NH
HOAcbenzene
CHO
JACS, 1952, 74, 4223
OH
OO
O
HH
Me
OONH
NaOH
O
O
Me
OH
HOOH
O
O
O
O
Me
Helv. Chim. Acta, 1950, 33, 2215
Bifunctional Enamine Catalysis: Generic Induction Platform
Use of proline or proline-type activation a widely exploited mode of ketone activation
R1
R
O
NH O
OH
X=Y
X Y HN
O
H
R
R'O
N NR
R
Amination
PhNO2
Nitro olefinaddition
H Me
MeO
Cross-Aldol
Org. Lett. 2001, 2423
Org. Lett. 2001, 573
Unconventional Reactivity Profiles Induced by Chiral Primary Amines Catalysis
Paolo Melchiorre,
Inst. Chem Research of Catalonia
Recent Advances in Stereoselectives Synthesis
Ilan Marek
Technion-Israel Institute of Technology
Directed Evolution of Enzymes: New Biocatalysts for Organic Synthesis
Nicholas J. Turner,
University of Manchester
Enantioselective Biocatalytic Oxidative Desymmetrization of Substituted Pyrrolidines
Seeking Fundamental Insights and Practical Reaction: Asymmetric Catalysis as a Synthetic and Mechanistic Tool
Eric Jacobsen,
Harvard University
Enantioselective Thiourea-Catalyzed Cationic Polycyclizations
Ruthenium Catalyzed Directing Group-Free C2-Selective Carbenoid Functionalization of Indoles by α-Aryldiazoesters
Org. Lett, 2010, 12, 604
Ruthenium Diversity: Alkynes, Carbenes and C-H Bonds
Pierre H. Dixneuf,
Rennes, Frances
Sequential Synthesis of Furans from Alkynes
National University of Malaysia
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