Transfer Hydrocyanation of α- and α,β-Substituted Styrenes Catalyzed by Boron Lewis Acids.

A straightforward gram-scale preparation of cyclohexa-1,4-diene-based hydrogen cyanide (HCN) surrogates is reported. These are bench-stable but formally release HCN and rearomatize when treated with Lewis acids. For BCl , the formation of the isocyanide adduct [(CN)BCl ] and the corresponding Wheland complex was verified by mass spectrometry. In the presence of 1,1-di- and trisubstituted alkenes, transfer of HCN from the surrogate to the C-C double bond occurs, affording highly substituted nitriles with Markovnikov selectivity. The success of this transfer hydrocyanation depends on the Lewis acid employed; catalytic amounts of BCl and (C F ) BCl are shown to be effective while B(C F ) and BF ⋅OEt are not.