ORGANIC
LETTERS
2012
Vol. 14, No. 4
1074–1077
Selenide Ions as Catalysts for Homo- and
Crossed-Tishchenko Reactions of
Expanded Scope
Simon P. Curran and Stephen J. Connon*
School of Chemistry, Centre for Synthesis and Chemical Biology, Trinity Biomedical
Sciences Institute, University of Dublin, Trinity College, Dublin 2, Ireland
Received December 23, 2011
ABSTRACT
Selenide ions have been shown to catalyze the Tishchenko reaction for the first time. These catalysts are superior to previously reported thiolate
analogues and promote the disproportionation of aldehydes with increased reaction rates and broader scope at lower catalyst loadings and
temperatures. Significantly improved catalyst performance was also observed in the aryl selenide mediated crossed intermolecular Tishchenko
reaction.
The Tishchenko reaction (in its simplest form) involves
the disproportionation of two aldehyde molecules to
generate a single coupled ester product.1 Several promo-
ters have been developed for this metal-ion-catalyzed2À6
Cannizarro-type7 process. However, it has been regarded
more as a mechanistic curiosity than as a powerful synthetic
tool by contemporary chemists, despite over a century of
research, largely due to a narrow substrate scope, which
until recently8 was limited (in an intermolecular context) to
the homocoupling of aldehydes, in often variable yields.9
Inspired by the mode of action of the glycolytic enzyme
glyceraldehyde-3-phosphate dehydrogenase, involving hy-
dride transfer from a hemithioacetal-based intermediate
(A, Scheme 1),10 we recently developed the first thiolate-
catalyzed Tishchenko processes (A, Scheme 1).11,12 The
smooth conversion of benzaldehyde (1) to the corresponding
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€
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10.1021/ol203439g
Published on Web 02/03/2012
2012 American Chemical Society