Issue 1, 2015

Mechanistic insights into hydroacylation with non-chelating aldehydes


The combination of a small-bite-angle diphosphine bis(dicyclohexylphosphino)methane (dcpm) and [Rh(cod)OMe]2 catalyses the hydroacylation of 2-vinylphenols with a wide range of non-chelating aldehydes. Here we present a detailed experimental study that elucidates the factors contributing to the broad aldehyde scope and high reactivity. A variety of catalytically relevant intermediates were isolated and a [Rh(dcpm)(vinylphenolate)] complex was identified as the major catalytically relevant species. A variety of off-cycle intermediates were also identified that can re-enter the catalytic cycle by substrate- or 1,5-cyclooctadiene-mediated pathways. Saturation kinetics with respect to the 2-vinylphenol were observed, and this may contribute to the high selectivity for hydroacylation over aldehyde decarbonylation. A series of deuterium labelling experiments and Hammett studies support the oxidative addition of Rh to the aldehyde C–H bond as an irreversible and turnover-limiting step. The small bite angle of dcpm is crucial for lowering the barrier of this step and providing excellent reactivity with a variety of aldehydes.

Graphical abstract: Mechanistic insights into hydroacylation with non-chelating aldehydes

Supplementary files

Article information

Article type
Edge Article
09 Jul 2014
27 Aug 2014
First published
22 Sep 2014
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2015,6, 174-180

Mechanistic insights into hydroacylation with non-chelating aldehydes

S. K. Murphy, A. Bruch and V. M. Dong, Chem. Sci., 2015, 6, 174 DOI: 10.1039/C4SC02026J

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