Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions

Natalia Zotova; Linda J. Broadbelt; Alan Armstrong; Donna G. Blackmond

doi:10.1016/j.bmcl.2009.03.112

Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions

Natalia Zotova, Linda J. Broadbelt, Alan Armstrong, Donna G. Blackmond^*

^*Corresponding author for this work

Chemical and Biological Engineering

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

64 Scopus citations

Abstract

Reaction progress kinetic analysis of the proline-mediated intermolecular aldol reaction shows that the rate depends on the concentrations of both the donor ketone1 and the electrophilic aldehyde 2, implying that enamine formation cannot be rate-determining. The observed kinetics and deuterium isotope effects are consistent with formation of the product iminium species as the rate-determining step.

Original language	English (US)
Pages (from-to)	3934-3937
Number of pages	4
Journal	Bioorganic and Medicinal Chemistry Letters
Volume	19
Issue number	14
DOIs	https://doi.org/10.1016/j.bmcl.2009.03.112
State	Published - Jul 15 2009

Keywords

Asymmetric catalysis
Kinetics
Mechanism
Organocatalysis
Proline

ASJC Scopus subject areas

Biochemistry
Molecular Medicine
Molecular Biology
Pharmaceutical Science
Drug Discovery
Clinical Biochemistry
Organic Chemistry

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10.1016/j.bmcl.2009.03.112

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title = "Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions",

abstract = "Reaction progress kinetic analysis of the proline-mediated intermolecular aldol reaction shows that the rate depends on the concentrations of both the donor ketone1 and the electrophilic aldehyde 2, implying that enamine formation cannot be rate-determining. The observed kinetics and deuterium isotope effects are consistent with formation of the product iminium species as the rate-determining step.",

keywords = "Asymmetric catalysis, Kinetics, Mechanism, Organocatalysis, Proline",

author = "Natalia Zotova and Broadbelt, {Linda J.} and Alan Armstrong and Blackmond, {Donna G.}",

note = "Funding Information: EPSRC funding (D.G.B./A.A. and D.G.B./L.J.B.) is gratefully acknowledged. L.J.B. was a Fullbright Fellow. D.G.B. holds a Royal Society Wolfson Research Merit Award. ",

year = "2009",

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doi = "10.1016/j.bmcl.2009.03.112",

language = "English (US)",

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TY - JOUR

T1 - Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions

AU - Zotova, Natalia

AU - Broadbelt, Linda J.

AU - Armstrong, Alan

AU - Blackmond, Donna G.

N1 - Funding Information: EPSRC funding (D.G.B./A.A. and D.G.B./L.J.B.) is gratefully acknowledged. L.J.B. was a Fullbright Fellow. D.G.B. holds a Royal Society Wolfson Research Merit Award.

PY - 2009/7/15

Y1 - 2009/7/15

N2 - Reaction progress kinetic analysis of the proline-mediated intermolecular aldol reaction shows that the rate depends on the concentrations of both the donor ketone1 and the electrophilic aldehyde 2, implying that enamine formation cannot be rate-determining. The observed kinetics and deuterium isotope effects are consistent with formation of the product iminium species as the rate-determining step.

AB - Reaction progress kinetic analysis of the proline-mediated intermolecular aldol reaction shows that the rate depends on the concentrations of both the donor ketone1 and the electrophilic aldehyde 2, implying that enamine formation cannot be rate-determining. The observed kinetics and deuterium isotope effects are consistent with formation of the product iminium species as the rate-determining step.

KW - Asymmetric catalysis

KW - Kinetics

KW - Mechanism

KW - Organocatalysis

KW - Proline

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M3 - Article

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VL - 19

SP - 3934

EP - 3937

JO - Bioorganic and Medicinal Chemistry Letters

JF - Bioorganic and Medicinal Chemistry Letters

SN - 0960-894X

IS - 14

ER -

Kinetic and mechanistic studies of proline-mediated direct intermolecular aldol reactions

Abstract

Keywords

ASJC Scopus subject areas

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