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

61 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

Access to Document

10.1016/j.bmcl.2009.03.112

Cite this

@article{e0b9c6c83a1142e69ed71a2726661c71,

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",

month = jul,

day = "15",

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

language = "English (US)",

volume = "19",

pages = "3934--3937",

journal = "Bioorganic and Medicinal Chemistry Letters",

issn = "0960-894X",

publisher = "Elsevier Limited",

number = "14",

}

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

UR - http://www.scopus.com/inward/record.url?scp=67649643720&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67649643720&partnerID=8YFLogxK

U2 - 10.1016/j.bmcl.2009.03.112

DO - 10.1016/j.bmcl.2009.03.112

M3 - Article

C2 - 19362473

AN - SCOPUS:67649643720

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

Access to Document

Other files and links

Fingerprint

Cite this