Literature Meeting - Charette Group

1
ACTIVATIONS BY HYDROGEN BONDING SUCCESS STORIES
Viresh H. Rawal
Eric N. Jacobsen
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 University Professor 1995.
The University of Chicago, Professor, 1995-.
1986-1988 Postdoctoral Fellow, MIT Professor K.
Barry Sharpless1982-1986 University of
California, Ph.D.Professor Robert G.
Bergman1978-1982 New York University B.S.
Professor Yorke E. Rhodes
Literature Meeting - Charette Group Marc K.
Janes December 6th 2004
2
ACTIVATIONS BY HYDROGEN BONDING OUTLINE

1. The Hydrogen Bond
2. Acid catalysis (concepts)
3. Recent examples in organic chemistry
4. Seminal work (from hine to jacobsen)
5. Diels-Alders (Rawal)
6. Other reactions

Literature Meeting - Charette Group Marc K.
Janes December 6th 2004
3
THE HYDROGEN BOND DEFINITIONS

• Pimentel and McClellan
• a hydrogen bond exists
• There is evidence of a bond
• 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
• It constitutes a local bond.
• X-H acts as proton donor to A.
• Etot Eelectrostatic Epolarization Echarge
  transfer Edespersion
• Eexchange repulsion

Steiner, ACIEE 2002, 48 (review)
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THE HYDROGEN BOND A REVIEW
Steiner, ACIEE 2002, 48 (review)
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THE HYDROGEN BOND ENERGY IN GAS PHASE
TO BE TAKEN WITH CAUTION NO MEDIUM EFFECT IN GAS
PHASE IDEAL GEOMETRY WAS USED IN
THE CALCULATIONS H-BONDS OFTEN FORM NETWORKS AND
ARE NOT ADDITIVE (CANNOT SPLIT ENERGY ON EACH
BOND)
Steiner, ACIEE 2002, 48 (review)
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THE HYDROGEN BOND A REVIEW
Steiner, ACIEE 2002, 48 (review)
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THE HYDROGEN BOND A REVIEW
Steiner, ACIEE 2002, 48 (review)
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TYPES OF BRONSTED ACID CATALYSIS
HYDROGEN BONDS ARE INVOLVED IN THE ACTIVATION OF
THE SUBSTRATE AND THESE HYDROGENS ARE
TRANSFERRED ONLY AT THE TRANSITION STATE
9
THE BRONSTED CATALYSIS LAW
Rate depends on H3O SAC Rate depends on HA
GAC
10
MODES OF CARBONYL ACTIVATION BY COORDINATION
Pihko, ACIEE 2004, 2062 (highlight)
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EXAMPLES OF INTERACTIONS
Etter, JACS 1988, 5896 Acc. Chem. Res. 1990,
120. Kelly, TL 1990, 3381.
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EXAMPLES OF INTERACTIONS
Radical allylation
Curran, JOC 1994, 3259 TL 1995, 6647.
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JACOBSEN (SIGMAN) STRECKER (must find a project
that works)
Jacobsen, JACS 1998, 1401
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JACOBSEN (SIGMAN) - STRECKER
Jacobsen, JACS 1998, 1401 ACIEE 2000, 1279
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JACOBSEN (SIGMAN) - STRECKER
Jacobsen, ACIEE 2000, 1279
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JACOBSEN (SIGMAN) STRECKER (MACHOISM)
Jacobsen, ACIEE 2000, 1279
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JACOBSEN (SIGMAN) - STRECKER
Jacobsen, ACIEE 2000, 1279
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JACOBSEN STRECKER ON KETOIMINES
1c
Jacobsen, OL 2000, 867
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JACOBSEN REACTION KINETICS
Model reaction
Previously optimal catalyst
Jacobsen, JACS 2002, 10012
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JACOBSEN KINETIC STUDY OF UREA CATALYST
INTERCEPT IS 1/vMAX Indicating that There is a
VMAX
Jacobsen, JACS 2002, 10012
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JACOBSEN REACTION KINETICS CONCLUSIONS
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
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JACOBSEN PROBES INTO BINDING (where are the
interactions?)
Jacobsen, JACS 2002, 10012
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JACOBSEN BINDING STUDY OF UREA CATALYST
Jacobsen, JACS 2002, 10012 SEE MARCELO IN JANUARY
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JACOBSEN BINDING STUDY OF UREA CATALYST
Jacobsen, JACS 2002, 10012 SEE MARCELO IN JANUARY
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JACOBSEN BINDING STUDY OF UREA CATALYST
3
Jacobsen, JACS 2002, 10012
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JACOBSEN IMINE GEOMETRY IN SOLUTION AND
REACTIVE FORM
ADDITION OF CATALYST
Only the Z Interacts!
Good reaction with fixed Z imine (ACIEE)
Unreactive Fixed E imine
Jacobsen, JACS 2002, 10012
27
JACOBSEN OUR FRIEND THE COMPUTER
Solvent has little effect on solution phase
structure (justification for gas phase
approximation)
Jacobsen, JACS 2002, 10012 SEE CLAUDE ANY TIME
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JACOBSEN BINDING STUDY OF UREA CATALYST
(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 accommodated within the optimal
geometry. (3) The N-substituent is also directed
away from the catalyst. However, its size is
restricted as a 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.
Adopts a well defined secondary structure in
solution
The last hypothesis leads to the prediction that
increasing the steric properties of the amino
acid/amide portion of the catalyst should lead to
higher enantioselectivity in the
hydrocyanation reactions.
Jacobsen, JACS 2002, 10012
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JACOBSEN UREA RATIONAL DESIGN
Jacobsen, JACS 2002, 10012
30
JACOBSEN UREA RATIONAL DESIGN (MACHOISM)
Jacobsen, JACS 2002, 10012
31
JACOBSEN MANNICH (NO STUDY)
Jacobsen, JACS 2002, 12964
32
JACOBSEN HYDROPHOSPHONYLATION (NO STUDY)
Jacobsen, JACS 2004, 4102
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JACOBSEN HYDROPHOSPHONYLATION (NO STUDY)
Jacobsen, JACS 2004, 4102
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JACOBSEN - PICTET-SPENGLER
Jacobsen, JACS 2004, 10558.
35
JACOBSEN - PICTET-SPENGLER (NO STUDY)
Jacobsen, JACS 2004, 10558.
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JACOBSEN - PICTET-SPENGLER (NO STUDY)
Jacobsen, JACS 2004, 10558.
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JORGENSEN REVIEW ON HDA
Warning, the following slide contains explicit
content
Jorgensen, ACIEE 2000, 3559
38
JORGENSEN REVIEW ON HDA
Jorgensen, ACIEE 2000, 3559
39
RAWAL LEWIS ACID CATALYZED DA (SALEN-Cr)
1-amino-3-siloxy-1,3-butadienes
Rawal JACS 2000, 7843 OL 2002, 1163 JACS 2002,
4628 (SUBTLE CHIRALITY)
40
RAWAL - HDA OF UNACTIVATED KETONES
Rawal, OL 2002, 3321
Rawal, JACS 2002, 4628
Rawal, JACS 2002, 4628
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RAWAL - REACTION OF UNACTIVATED KETONES
Not due to prensence of DCl
Rawal, OL 2002, 3321
42
RAWAL VERY REACTIVE DIENE
Rawal, OL 2002, 3321 Jurczak, SYNTHESIS 1979, 41
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RAWAL HDA SOLVENT SCAN
Rawal, JACS 2002, 9662
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RAWAL - HDA OF UNACTIVATED KETONES
Dihydropone
Solvolysis Product
Rawal, JACS 2002, 9662
45
RAWAL FIRST GENERAL HDA FOR UNACTIVATED KETONES
Rawal, JACS 2002, 9662
46
MACMILLAN/HOUK/LIST ORGANOCATALYSIS OTHER THAN
H BOND
MacMillan, JACS 2000, 4243 TL 2003, 2475
Houk-List, JACS 2003, 16 JACS 2003, 2475
47
BRADDOCK PHANOLS FOR DA (NOT ENANTIOSELECTIVE)
Braddock, Synlett 2003, 1121
48
GÖBEL H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
49
RAWAL - FIRST ASYMM. HDA THROUGH HYDROGEN BONDING
Ar 1-naphtyl
Rawal, Nature 2003, 146
50
RAWAL - ALL CARBON ASYMM. DA CAT. BY H-BONDING
Rawal, PNAS 2004, 5846
51
ALL CARBON DA CAT. BY HYDROGEN BONDING
Rawal, PNAS 2004, 5846
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ALL CARBON DA CAT. BY HYDROGEN BONDING
More persistent hydrogen bond at lower
temperatures
Rawal, PNAS 2004, 5846
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RAWAL - ALL CARBON DA CAT. BY HYDROGEN BONDING
REACTION WORK BEST WITH ALPHA SUBSTITUTION MACMIL
LAN BEST WITH BETA SUBSTITUTION (COMPLEMENTARY)
Rawal, PNAS 2004, 5846
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THE END
Pioneers for a new mode of asymmetric catalysis
involving one one the most important bond in
nature?
Viresh H. Rawal
Eric N. Jacobsen
Literature Meeting - Charette Group Marc K.
Janes December 6th 2004
55
T
Schaus, JACS 2003, 12094
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TITLE
Ref or note
57
GÖBEL H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
58
GÖBEL H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
59
GÖBEL H BOND ASSISTED ASYMMETRIC DA
Göbel, OL 2000, 179
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TYPES OF ACID CATALYSIS
Note or ref
61
DOUBLE HYDROGEN BONDING - SEMINAL WORK
Hine, JOC 1985, 5096 JOC 1987, 2083 Kelly, TL
1990, 2083
62
TITLE
Schreiner, Chem. Soc. Rev. 2003, 289 Chem. Euro.
J. 2003, 407