Skip to main content
eScholarship
Open Access Publications from the University of California

UC Irvine

UC Irvine Previously Published Works bannerUC Irvine

Mechanistic insights into hydroacylation with non-chelating aldehydes

Abstract

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.

Many UC-authored scholarly publications are freely available on this site because of the UC's open access policies. Let us know how this access is important for you.

Main Content
For improved accessibility of PDF content, download the file to your device.
Current View