Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling.

Abstract

The stibinidene ArSbI (Ar = [2,6-(tBuN═CH)2-C6H3], 1) reacts with S2Tol2 (Tol = p-tolyl) to form ArSbIII(STol)2 (2), which upon treatment with pinacolborane, regenerates 1. These processes unveil an unprecedented antimony redox catalysis involving Sb(I)/Sb(III) cycling for the hydroboration of organic disulfides. Elementary reaction studies and density functional theory calculations support that the catalysis mimics transition metal processes, proceeding through oxidative addition, ligand metathesis, and reductive elimination. The thiophenols and sulfidoborates generated from the hydroboration of disulfides react in situ with α,β-unsaturated carbonyl compounds with the assistance of 1 as a base catalyst. These tandem reactions establish a one-pot synthetic method for β-sulfido carbonyl compounds, in which a stibinidene functions as a redox catalyst and a base catalyst successively, illustrating the versatility and efficiency of antimony catalysis in organic synthesis.