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Transfer Hydrocyanation of α‐ and α,β‐Substituted Styrenes Catalyzed by Boron Lewis Acids
Author(s) -
Orecchia Patrizio,
Yuan Weiming,
Oestreich Martin
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813853
Subject(s) - hydrocyanation , chemistry , lewis acids and bases , adduct , nitrile , catalysis , medicinal chemistry , hydrogen cyanide , isocyanide , cyanide , selectivity , organic chemistry
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 3 , the formation of the isocyanide adduct [(CN)BCl 3 ] − 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 3 and (C 6 F 5 ) 2 BCl are shown to be effective while B(C 6 F 5 ) 3 and BF 3 ⋅OEt 2 are not.