Probing the limits of rate acceleration mediated by hydrogen bonds

R M Cowie; S M Turega; Douglas Philp

doi:10.1021/ol061290c

Probing the limits of rate acceleration mediated by hydrogen bonds

R M Cowie, S M Turega, Douglas Philp

Research output: Contribution to journal › Article › peer-review

Abstract

A simple receptor and substrate are used to probe the relationship between transition-state charge and the level of rate acceleration that can be created by stabilizing the transition state through hydrogen bonding. Pericyclic reactions are accelerated less than 2-fold by the receptor, whereas a conjugate addition reaction is accelerated more than 30-fold. Therefore, substrate polarization by hydrogen bonding would only appear to be effective for reactions that generate significant charge at the transition state.

Original language	English
Pages (from-to)	5179-5183
Number of pages	4
Journal	Organic Letters
Volume	8
Issue number	23
DOIs	https://doi.org/10.1021/ol061290c
Publication status	Published - 9 Nov 2006

Keywords

DIELS-ALDER REACTION
ANTIBODY-CATALYSIS
MACROPHOMATE SYNTHASE
CHORISMATE MUTASE
CYCLOADDITION REACTION
DIPOLAR CYCLOADDITION
REACTION-MECHANISM
RECOGNITION
REARRANGEMENT
BIOSYNTHESIS

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10.1021/ol061290c

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title = "Probing the limits of rate acceleration mediated by hydrogen bonds",

abstract = "A simple receptor and substrate are used to probe the relationship between transition-state charge and the level of rate acceleration that can be created by stabilizing the transition state through hydrogen bonding. Pericyclic reactions are accelerated less than 2-fold by the receptor, whereas a conjugate addition reaction is accelerated more than 30-fold. Therefore, substrate polarization by hydrogen bonding would only appear to be effective for reactions that generate significant charge at the transition state.",

keywords = "DIELS-ALDER REACTION, ANTIBODY-CATALYSIS, MACROPHOMATE SYNTHASE, CHORISMATE MUTASE, CYCLOADDITION REACTION, DIPOLAR CYCLOADDITION, REACTION-MECHANISM, RECOGNITION, REARRANGEMENT, BIOSYNTHESIS",

author = "Cowie, {R M} and Turega, {S M} and Douglas Philp",

year = "2006",

month = nov,

day = "9",

doi = "10.1021/ol061290c",

language = "English",

volume = "8",

pages = "5179--5183",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society (ACS)",

number = "23",

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T1 - Probing the limits of rate acceleration mediated by hydrogen bonds

AU - Cowie, R M

AU - Turega, S M

AU - Philp, Douglas

PY - 2006/11/9

Y1 - 2006/11/9

N2 - A simple receptor and substrate are used to probe the relationship between transition-state charge and the level of rate acceleration that can be created by stabilizing the transition state through hydrogen bonding. Pericyclic reactions are accelerated less than 2-fold by the receptor, whereas a conjugate addition reaction is accelerated more than 30-fold. Therefore, substrate polarization by hydrogen bonding would only appear to be effective for reactions that generate significant charge at the transition state.

AB - A simple receptor and substrate are used to probe the relationship between transition-state charge and the level of rate acceleration that can be created by stabilizing the transition state through hydrogen bonding. Pericyclic reactions are accelerated less than 2-fold by the receptor, whereas a conjugate addition reaction is accelerated more than 30-fold. Therefore, substrate polarization by hydrogen bonding would only appear to be effective for reactions that generate significant charge at the transition state.

KW - DIELS-ALDER REACTION

KW - ANTIBODY-CATALYSIS

KW - MACROPHOMATE SYNTHASE

KW - CHORISMATE MUTASE

KW - CYCLOADDITION REACTION

KW - DIPOLAR CYCLOADDITION

KW - REACTION-MECHANISM

KW - RECOGNITION

KW - REARRANGEMENT

KW - BIOSYNTHESIS

UR - http://www.scopus.com/inward/record.url?scp=33845254964&partnerID=8YFLogxK

U2 - 10.1021/ol061290c

DO - 10.1021/ol061290c

M3 - Article

SN - 1523-7060

VL - 8

SP - 5179

EP - 5183

JO - Organic Letters

JF - Organic Letters

IS - 23

ER -

Probing the limits of rate acceleration mediated by hydrogen bonds

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BBSRC B20102: Probing the relative efficiencies of direct and reciprocal replication strategies

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Probing the limits of rate acceleration mediated by hydrogen bonds

Abstract

Keywords

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BBSRC B20102: Probing the relative efficiencies of direct and reciprocal replication strategies

Cite this