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Transfer Hydrocyanation of α- and α,β-Substituted Styrenes Catalyzed by Boron Lewis Acids
Patrizio Orecchia1, Weiming Yuan1, Martin Oestreich1
1Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
Abstract:
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 BCl3 , the formation of the isocyanide adduct [(CN)BCl3 ]- 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 BCl3 and (C6 F5 )2 BCl are shown to be effective while B(C6 F5 )3 and BF3 ⋅OEt2 are not.
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