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Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation
Author(s) -
Bini Laura,
Pidko Evgeny A.,
Müller Christian,
van Santen Rutger A.,
Vogt Dieter
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200802611
Subject(s) - hydrocyanation , regioselectivity , lewis acids and bases , chemistry , styrene , catalysis , reaction mechanism , deuterium , organic chemistry , copolymer , polymer , physics , quantum mechanics
Abstract According to present knowledge, the Ni‐catalyzed hydrocyanation of styrene leads predominantly to the branched product 2‐phenylpropionitrile (98 %). We observed a dramatic inversion of the regioselectivity upon addition of a Lewis acid. Up to 83 % of the linear product 3‐phenylpropionitrile was obtained by applying phosphite ligands in the presence of AlCl 3 . The mechanism of the Ni‐catalyzed reaction and the influence of additional Lewis acids have been investigated by means of deuterium labeling experiments, NMR studies, and DFT calculations. Furthermore, the behavior of different Lewis acids, such as CuCN, could be rationalized and predicted by DFT calculations.