The polar effect on the regiochemistry of nucleophilic substitution of trifluoromethylated pi-allylpalladium complex

Okano, T; Matsubara, H; Kusukawa, T; Fujita, M

HERO ID

4936239

Reference Type

Journal Article

Year

2003

HERO ID 4936239
In Press No
Year 2003
Title The polar effect on the regiochemistry of nucleophilic substitution of trifluoromethylated pi-allylpalladium complex
Authors Okano, T; Matsubara, H; Kusukawa, T; Fujita, M
Journal Journal of Organometallic Chemistry
Volume 676
Issue 1-2
Page Numbers 43-48
Abstract Allylic nucleophilic substitution of trifluoromethyl-group substituted cinnamyl carbonate with diethyl malonate anion in the presence of palladium complex catalyst gave regio- and stereo selectively the S(N)2' product. The regiochemistry caused by the polar effect of trifluoromethyl group was opposite to the methylated cinnamyl substrate in a similar steric environment. The sterically more hindered mesityl and tert-butyl substrates than phenyl derivative also gave the products reacted at the more hindered sites. Although o-substituted substrates expecting intramolecular coordination to affect regiochemistry were examined, no alternative regioisomers were detected. (C) 2003 Elsevier Science B.V. All rights reserved.
Doi 10.1016/S0022-328X(03)00262-6
Wosid WOS:000183589000005
Is Certified Translation No
Dupe Override No
Is Public Yes
Keyword pi-allylpalladium complexes; regiochemistry; trifluoromethyl group; alpha-acceptor