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. 2014 Jul 29;111(30):10917-21.
doi: 10.1073/pnas.1407484111. Epub 2014 Jul 7.

Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

Manuel Pérez  1 , Christopher B Caputo  1 , Roman Dobrovetsky  1 , Douglas W Stephan  2
Affiliations

Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

Manuel Pérez et al. Proc Natl Acad Sci U S A. .

Abstract

A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C6F5)3PF][B(C6F5)4] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metal-free catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations.

Keywords: fluorophosphonium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Fig. 1.
Fig. 1.
Proposed mechanistic pathways for dehydrocoupling of silane and amine and transfer hydrogenation of olefins (experiment: R3Si = Et3Si, ClMe2Si, Ph3Si, PhMe2Si; Ar2NH = Ph2NH, p-Me(C6H4)2NH; calculations: R3Si = Me3Si; Ar = Ph). Gibbs free energies and enthalpies in parentheses for every step are provided in kilocalories per mole.
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