Stoichiometric and catalytic isomerization of alkenylboranes using bulky Lewis bases

Abstract

1,1-Carboboration of alkynes with boranes R′B(C₆F₅)₂ (R′ = (CH₂)₃Ph, C₆F₅) affords mixtures of the E and Z isomers of RCH = CR′B(C₆F₅)₂ (R = (CH₂)₂Me, (CH₂)₃Me, (CH₂)₂Ph, CH₂CHMe₂, CHMe₂, CMe₃, CH₂OMe, CH₂N(CO)₂C₆H₄), treatment of these alkenylboranes with stoichiometric or catalytic amounts of tBu₂PH or other donors are shown to induce isomerization. The proposed mechanism involving a zwitterionic borataalkene intermediate is supported by computations.