Mechanistic insights into the triazolylidene-catalysed Stetter and benzoin reactions: role of the N-aryl substituent

被引：114

作者：

Collett, Christopher J. ^{[1
]}

Massey, Richard S. ^{[2
]}

Maguire, Oliver R. ^{[2
]}

Batsanov, Andrei S. ^{[2
]}

O'Donoghue, AnnMarie C. ^{[2
]}

Smith, Andrew D. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

[2] Univ Durham, Univ Sci Labs, Dept Chem, Durham DH1 3LE, England

来源：

CHEMICAL SCIENCE | 2013年 / 4卷 / 04期

基金：

英国工程与自然科学研究理事会;

关键词：

HETEROCYCLIC CARBENE; ALPHA; BETA-UNSATURATED ALDEHYDES; TRIAZOLIUM SALTS; NUCLEOPHILIC-ADDITION; BRESLOW INTERMEDIATE; THIAZOLIUM SALTS; THIAMINE ACTION; UMPOLUNG; GENERATION; ACID;

D O I：

10.1039/c2sc22137c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The in situ observation, isolation and reversible formation of intermediate 3-(hydroxybenzyl) azolium salts derived from NHC addition to a range of substituted benzaldehydes is probed. Equilibrium constants for the formation of these 3-(hydroxybenzyl) azolium salts, as well as rate constants of hydrogen-deuterium exchange (k(ex)) at C(alpha) of these intermediates for a range of N-aryl triazolinylidenes is reported. These combined studies give insight into the preference of N-pentafluorophenyl NHCs to participate in benzoin and Stetter reaction processes.

引用

页码：1514 / 1522

页数：9

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