Mechanism of the [(NHC)Au-I]-Catalyzed Rearrangement of Allylic Acetates. A DFT Study

Christophe Gourlaouen; Nicolas Marion; Steven Patrick Nolan; Feliu Maseras

doi:10.1021/ol802430m

Mechanism of the [(NHC)Au-I]-Catalyzed Rearrangement of Allylic Acetates. A DFT Study

Christophe Gourlaouen, Nicolas Marion, Steven Patrick Nolan, Feliu Maseras

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

Abstract

The DFT study of the mechanism of the rearrangement of H2C=CHC(CH3)OCOCH3 to (CH3)(H)C=CHCH2OCOCH3 catalyzed by [(NHC)Au](+) (NHC = N-heterocyclic carbene) shows that a low energy path exists, with a barrier of 14.2 kcal.mol(-1), going through a six-membered ring acetoxonium Intermediate and where gold coordinates one of the carbon atoms In the alkene system. The qualitative features of the mechanism are not affected by the Introduction of other NHC ligands, counterions, or solvation effects.

Original language	English
Pages (from-to)	81-84
Number of pages	4
Journal	Organic Letters
Volume	11
Issue number	1
DOIs	https://doi.org/10.1021/ol802430m
Publication status	Published - 1 Jan 2009

Keywords

GOLD CATALYSIS
HETEROCYCLIC CARBENES
PROPARGYLIC ESTERS
CYCLOPROPANATION
ACTIVATION
ACCESS
SHIFTS
TANDEM

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abstract = "The DFT study of the mechanism of the rearrangement of H2C=CHC(CH3)OCOCH3 to (CH3)(H)C=CHCH2OCOCH3 catalyzed by [(NHC)Au](+) (NHC = N-heterocyclic carbene) shows that a low energy path exists, with a barrier of 14.2 kcal.mol(-1), going through a six-membered ring acetoxonium Intermediate and where gold coordinates one of the carbon atoms In the alkene system. The qualitative features of the mechanism are not affected by the Introduction of other NHC ligands, counterions, or solvation effects.",

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author = "Christophe Gourlaouen and Nicolas Marion and Nolan, {Steven Patrick} and Feliu Maseras",

year = "2009",

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doi = "10.1021/ol802430m",

language = "English",

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journal = "Organic Letters",

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TY - JOUR

T1 - Mechanism of the [(NHC)Au-I]-Catalyzed Rearrangement of Allylic Acetates. A DFT Study

AU - Gourlaouen, Christophe

AU - Marion, Nicolas

AU - Nolan, Steven Patrick

AU - Maseras, Feliu

PY - 2009/1/1

Y1 - 2009/1/1

N2 - The DFT study of the mechanism of the rearrangement of H2C=CHC(CH3)OCOCH3 to (CH3)(H)C=CHCH2OCOCH3 catalyzed by [(NHC)Au](+) (NHC = N-heterocyclic carbene) shows that a low energy path exists, with a barrier of 14.2 kcal.mol(-1), going through a six-membered ring acetoxonium Intermediate and where gold coordinates one of the carbon atoms In the alkene system. The qualitative features of the mechanism are not affected by the Introduction of other NHC ligands, counterions, or solvation effects.

AB - The DFT study of the mechanism of the rearrangement of H2C=CHC(CH3)OCOCH3 to (CH3)(H)C=CHCH2OCOCH3 catalyzed by [(NHC)Au](+) (NHC = N-heterocyclic carbene) shows that a low energy path exists, with a barrier of 14.2 kcal.mol(-1), going through a six-membered ring acetoxonium Intermediate and where gold coordinates one of the carbon atoms In the alkene system. The qualitative features of the mechanism are not affected by the Introduction of other NHC ligands, counterions, or solvation effects.

KW - GOLD CATALYSIS

KW - HETEROCYCLIC CARBENES

KW - PROPARGYLIC ESTERS

KW - CYCLOPROPANATION

KW - ACTIVATION

KW - ACCESS

KW - SHIFTS

KW - TANDEM

UR - http://www.scopus.com/inward/record.url?scp=58949100235&partnerID=8YFLogxK

U2 - 10.1021/ol802430m

DO - 10.1021/ol802430m

M3 - Article

SN - 1523-7060

VL - 11

SP - 81

EP - 84

JO - Organic Letters

JF - Organic Letters

IS - 1

ER -

Mechanism of the [(NHC)Au-I]-Catalyzed Rearrangement of Allylic Acetates. A DFT Study

Abstract

Keywords

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