title: Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis.
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.
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, ON, Canada M5S 3H6.
authors.forename: Manuel
authors.initials: M
authors.lastname: Pérez
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, ON, Canada M5S 3H6.
authors.forename: Christopher B
authors.initials: CB
authors.lastname: Caputo
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, ON, Canada M5S 3H6.
authors.forename: Roman
authors.initials: R
authors.lastname: Dobrovetsky
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, ON, Canada M5S 3H6 dstephan@chem.utoronto.ca.
authors.forename: Douglas W
authors.initials: DW
authors.lastname: Stephan
keywords: fluorophosphonium