literature meeting - charette group – marc k. janes – december 6 th 2004

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


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


THE HYDROGEN BOND – A 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)


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 (MACHOISM)

Jacobsen, OL 2000, 867

JACOBSEN – STRECKER ON KETOIMINES

1c

NH

N

HO

tBu O tBu

O

NH

OHN

tBu

O

Ph


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 – KINETIC STUDY OF UREA CATALYST

INTERCEPTIS 1/vMAX

Indicating thatThere is a VMAX


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 – PROBES INTO BINDING (where are the interactions?)

Jacobsen, JACS 2002, 10012; SEE MARCELO IN JANUARY

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 – 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)



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 – UREA RATIONAL DESIGN


JACOBSEN – UREA RATIONAL DESIGN (MACHOISM)


JACOBSEN – MANNICH (NO STUDY)


JACOBSEN – HYDROPHOSPHONYLATION (NO STUDY)

Jacobsen, JACS 2004, 10558.

JACOBSEN - PICTET-SPENGLER

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, 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 – HDA SOLVENT SCAN


RAWAL - HDA OF UNACTIVATED KETONES

Dihydropone

O

NMe2

SolvolysisProduct :


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


ALL CARBON DA CAT. BY HYDROGEN BONDING


ALL CARBON DA CAT. BY HYDROGEN BONDING

More persistent hydrogen bondat lower temperatures


RAWAL - ALL CARBON DA CAT. BY HYDROGEN BONDING

REACTION WORK BEST WITH ALPHA SUBSTITUTION;MACMILLAN: BEST WITH BETA SUBSTITUTION (COMPLEMENTARY)


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

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

literature meeting - charette group – marc k. janes – december 6 th 2004

Documents

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