TY - JOUR
T1 - Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation
AU - Bini, Laura
AU - Pidko, Evgeny A.
AU - Muller, Christian
AU - van Santen, Rutger A.
AU - Vogt, Dieter
PY - 2009
Y1 - 2009
N2 - 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 AlCl3. 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.
AB - 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 AlCl3. 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.
U2 - 10.1002/chem.200802611
DO - 10.1002/chem.200802611
M3 - Article
SN - 0947-6539
VL - 15
SP - 8768
EP - 8778
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 35
ER -