literature meeting - charette group – marc k. janes – december 6 th 2004
DESCRIPTION
ACTIVATIONS BY HYDROGEN BONDING – SUCCESS STORIES. Viresh H. Rawal. Eric N. Jacobsen. 1986-1988 : Postdoctoral Fellow, MIT Professor K. Barry Sharpless 1982-1986 : University of California, Ph.D. Professor Robert G. Bergman 1978-1982 : New York University B.S. Professor Yorke E. Rhodes. - PowerPoint PPT PresentationTRANSCRIPT
Literature Meeting - Charette Group – Marc K. Janes – December 6th 2004
ACTIVATIONS BY HYDROGEN BONDING – SUCCESS STORIES
Born Rajkot, India, 1958.
University of Connecticut, B.S., 1980.
University of Pennsylvania, Ph.D., 1986.
Columbia University, Postdoctoral Fellow, 1986-1988.
The Ohio State UniversityProfessor 1995.
The University of Chicago, Professor, 1995-.
1986-1988: Postdoctoral Fellow, MITProfessor K. Barry Sharpless
1982-1986: University of California, Ph.D.Professor Robert G. Bergman
1978-1982: New York University B.S. Professor Yorke E. Rhodes
Eric N. Jacobsen Viresh H. Rawal
Literature Meeting - Charette Group – Marc K. Janes – December 6th 2004
ACTIVATIONS BY HYDROGEN BONDING – OUTLINE
1) The Hydrogen Bond 2) Acid catalysis (concepts)3) Recent examples in organic chemistry
1) Seminal work (from hine to jacobsen)2) Diels-Alders (Rawal)3) Other reactions
Steiner, ACIEE 2002, 48 (review)
THE HYDROGEN BOND – DEFINITIONS
Pimentel and McClellan:‘’…a hydrogen bond exists1) There is evidence of a bond2) There is evidence that this bond sterically involves
a hydrogen atom already bonded to another atom…’’.
Drawback: May include van der Waals interactions and agostic
interactions (3 center 2 electrons).
Proposed definition:
An X-H - - - A interaction is called a ‘’hydrogen bond’’:
1. It constitutes a local bond.2. X-H acts as proton donor to A.
Etot = Eelectrostatic+ Epolarization + Echarge transfer + Edespersion
+ Eexchange repulsion
Steiner, ACIEE 2002, 48 (review)
THE HYDROGEN BOND – A REVIEW
Steiner, ACIEE 2002, 48 (review)
THE HYDROGEN BOND – ENERGY IN GAS PHASE
TO BE TAKEN WITHCAUTION
NO MEDIUM EFFECTIN GAS PHASE
IDEAL GEOMETRYWAS USED IN THE
CALCULATIONS
H-BONDS OFTEN FORMNETWORKS AND ARE NOTADDITIVE (CANNOT SPLITENERGY ON EACH BOND)
Steiner, ACIEE 2002, 48 (review)
THE HYDROGEN BOND – A REVIEW
Steiner, ACIEE 2002, 48 (review)
THE HYDROGEN BOND – A REVIEW
TYPES OF BRONSTED ACID CATALYSIS
HYDROGEN BONDS ARE INVOLVEDIN THE ACTIVATION OF THE SUBSTRATE
AND THESE HYDROGENS ARE TRANSFERREDONLY AT THE TRANSITION STATE
THE BRONSTED CATALYSIS LAW
Rate depends on [H3O+] : SACRate depends on [HA] : GAC
Pihko, ACIEE 2004, 2062 (highlight)
MODES OF CARBONYL ACTIVATION BY COORDINATION
Etter, JACS 1988, 5896; Acc. Chem. Res. 1990, 120. Kelly, TL 1990, 3381.
EXAMPLES OF INTERACTIONS
Curran, JOC 1994, 3259; TL 1995, 6647.
Radical allylation
EXAMPLES OF INTERACTIONS
Jacobsen, JACS 1998, 1401
JACOBSEN (SIGMAN) – STRECKER (must find a project that works…)
Jacobsen, JACS 1998, 1401; ACIEE 2000, 1279
JACOBSEN (SIGMAN) - STRECKER
Jacobsen, ACIEE 2000, 1279
JACOBSEN (SIGMAN) - STRECKER
Jacobsen, ACIEE 2000, 1279
JACOBSEN (SIGMAN) – STRECKER (MACHOISM)
Jacobsen, ACIEE 2000, 1279
JACOBSEN (SIGMAN) - STRECKER
Jacobsen, OL 2000, 867
JACOBSEN – STRECKER ON KETOIMINES
1c
NH
N
HO
tBu O tBu
O
NH
OHN
tBu
O
Ph
Jacobsen, JACS 2002, 10012
JACOBSEN – REACTION KINETICS
N
H
NH
CN
MeO MeO
Catalyst
HCN
NH
N
HO
tBu O tBu
O
NH
OHN
tBu
O
Ph
Model reaction Previously optimal catalyst
Jacobsen, JACS 2002, 10012
JACOBSEN – KINETIC STUDY OF UREA CATALYST
INTERCEPTIS 1/vMAX
Indicating thatThere is a VMAX
Jacobsen, JACS 2002, 10012
JACOBSEN – REACTION KINETICS CONCLUSIONS
N
H
NH
CN
MeO MeO
Catalyst
HCN
NH
N
HO
tBu O tBu
O
NH
OHN
tBu
O
Ph
Model reaction Previously optimal catalyst
- 1st order in HCN and Catalyst-Saturation kinetics of imine (proven by Lineweaver Burk)- Obeys Michaelis-Meten kinetics (steady state kinetics)
Implicates the reversible formation of an IMINE – CATALYST COMPLEX
Jacobsen, JACS 2002, 10012
JACOBSEN – PROBES INTO BINDING (where are the interactions?)
Jacobsen, JACS 2002, 10012; SEE MARCELO IN JANUARY
JACOBSEN – BINDING STUDY OF UREA CATALYST
Jacobsen, JACS 2002, 10012; SEE MARCELO IN JANUARY
JACOBSEN – BINDING STUDY OF UREA CATALYST
Jacobsen, JACS 2002, 10012
JACOBSEN – BINDING STUDY OF UREA CATALYST
NH
N
HO
tBu O tBu
O
NH
O
Bn2N
tBu
O
N
H
Ph14 N
H
Ph15
3
Jacobsen, JACS 2002, 10012
JACOBSEN – IMINE GEOMETRY IN SOLUTION AND REACTIVE FORM
N
OMeN
OMe
E Z20:1
NH
N
HO
tBu O tBu
O
NH
OHN
tBu
O
Ph
Only the ZInteracts!
Good reaction with fixed Z imine (ACIEE) UnreactiveFixed E imine
ADDITION OF CATALYST
N
Jacobsen, JACS 2002, 10012; SEE CLAUDE ANY TIME
JACOBSEN – OUR FRIEND THE COMPUTER
Solvent has little effect on solution phase structure(justification for gas phase approximation)
Jacobsen, JACS 2002, 10012
JACOBSEN – BINDING STUDY OF UREA CATALYST
NH
N
HO
tBu O tBu
O
NH
OHN
tBu
O
Ph
Adopts a well defined secondary structurein solution
(1) The large group on the imine carbon is directed away from the catalyst and into solvent (Figure 1B); this serves to explain why 1 catalyzes hydrocyanation of most aldimines with high ee, regardless of the steric and electronic properties of the substrate. (2) The small group (H for aldimines, Me for methylketoimines) is aimed directly into the catalyst; ketoimines bearing larger substituents are poor substrates for the reaction,2c presumably because they cannot be accommodatedwithin the optimal geometry. (3) The N-substituent is alsodirected away from the catalyst. However, its size is restricted asa result of the requirement to access the Z-isomer of the imine. (4) On the basis of the observed sense of stereoinduction, addition of HCN takes place over the diaminocyclohexane portion of the catalyst (i.e., from the right-hand side in Figure 1C) and away from the amino acid/amide portion.
The last hypothesis leads to the prediction that increasing thesteric properties of the amino acid/amide portion of the catalystshould lead to higher enantioselectivity in the hydrocyanationreactions.
Jacobsen, JACS 2002, 10012
JACOBSEN – UREA RATIONAL DESIGN
Jacobsen, JACS 2002, 10012
JACOBSEN – UREA RATIONAL DESIGN (MACHOISM)
Jacobsen, JACS 2002, 12964
JACOBSEN – MANNICH (NO STUDY)
Jacobsen, JACS 2004, 4102
JACOBSEN – HYDROPHOSPHONYLATION (NO STUDY)
Jacobsen, JACS 2004, 4102
JACOBSEN – HYDROPHOSPHONYLATION (NO STUDY)
Jacobsen, JACS 2004, 10558.
JACOBSEN - PICTET-SPENGLER
Jacobsen, JACS 2004, 10558.
JACOBSEN - PICTET-SPENGLER (NO STUDY)
Jacobsen, JACS 2004, 10558.
JACOBSEN - PICTET-SPENGLER (NO STUDY)
Jorgensen, ACIEE 2000, 3559
JORGENSEN – REVIEW ON HDA
Warning, the following slidecontains explicit content
Jorgensen, ACIEE 2000, 3559
JORGENSEN – REVIEW ON HDA
Rawal JACS 2000, 7843; OL 2002, 1163; JACS 2002, 4628 (SUBTLE CHIRALITY)
RAWAL – LEWIS ACID CATALYZED DA (SALEN-Cr)
1-amino-3-siloxy-1,3-butadienes
Rawal, JACS 2002, 4628
RAWAL - HDA OF UNACTIVATED KETONES
Rawal, OL 2002, 3321
Rawal, JACS 2002, 4628
Rawal, OL 2002, 3321
RAWAL - REACTION OF UNACTIVATED KETONES
Not due to prensence of DCl
Rawal, OL 2002, 3321; Jurczak, SYNTHESIS 1979, 41
RAWAL – VERY REACTIVE DIENE
TBSO
NMe2
O
PhHO
TBSO
NMe2
PhCDCl3rt, 2h
100%+
MeO O
PhH
OMeO
+20kbar
50oC Ph
Rawal, JACS 2002, 9662
RAWAL – HDA SOLVENT SCAN
Rawal, JACS 2002, 9662
RAWAL - HDA OF UNACTIVATED KETONES
Dihydropone
O
NMe2
SolvolysisProduct :
Rawal, JACS 2002, 9662
RAWAL – FIRST GENERAL HDA FOR UNACTIVATED KETONES
TBSO
NMe2
O
O
O+ Subst'
Subst
nSubst
Houk-List, JACS 2003, 16; JACS 2003, 2475
MACMILLAN/HOUK/LIST – ORGANOCATALYSIS OTHER THAN H BOND
MacMillan, JACS 2000, 4243; TL 2003, 2475
Braddock, Synlett 2003, 1121
BRADDOCK – PHANOLS FOR DA (NOT ENANTIOSELECTIVE)
Göbel, OL 2000, 179
GÖBEL – H BOND ASSISTED ASYMMETRIC DA
Rawal, Nature 2003, 146
RAWAL - FIRST ASYMM. HDA THROUGH HYDROGEN BONDING
Ar = 1-naphtyl
Rawal, PNAS 2004, 5846
RAWAL - ALL CARBON ASYMM. DA CAT. BY H-BONDING
Rawal, PNAS 2004, 5846
ALL CARBON DA CAT. BY HYDROGEN BONDING
Rawal, PNAS 2004, 5846
ALL CARBON DA CAT. BY HYDROGEN BONDING
More persistent hydrogen bondat lower temperatures
Rawal, PNAS 2004, 5846
RAWAL - ALL CARBON DA CAT. BY HYDROGEN BONDING
REACTION WORK BEST WITH ALPHA SUBSTITUTION;MACMILLAN: BEST WITH BETA SUBSTITUTION (COMPLEMENTARY)
Literature Meeting - Charette Group – Marc K. Janes – December 6th 2004
THE END
Eric N. JacobsenViresh H. Rawal
Pioneers for a new mode of asymmetric catalysis involving one one the most important bond in nature?
Schaus, JACS 2003, 12094
T
Ref or note
TITLE
Göbel, OL 2000, 179
GÖBEL – H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
GÖBEL – H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
GÖBEL – H BOND ASSISTED ASYMMETRIC DA
Note or ref
TYPES OF ACID CATALYSIS
Hine, JOC 1985, 5096; JOC 1987, 2083; Kelly, TL 1990, 2083
DOUBLE HYDROGEN BONDING - SEMINAL WORK
OO
NH
OHO NEt2
catalyst
butanone+
Schreiner, Chem. Soc. Rev. 2003, 289; Chem. Euro. J. 2003, 407
TITLE