Premium
Chemo‐ and Regioselective C(sp 3 )H Arylation of Unactivated Allylarenes by Deprotonative Cross‐Coupling
Author(s) -
Hussain Nusrah,
Frensch Gustavo,
Zhang Jiadi,
Walsh Patrick J.
Publication year - 2014
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.201309084
Subject(s) - transmetalation , regioselectivity , deprotonation , chemistry , reagent , aryl , catalysis , heck reaction , palladium , base (topology) , medicinal chemistry , coupling (piping) , combinatorial chemistry , reductive elimination , coupling reaction , organic chemistry , materials science , ion , mathematics , mathematical analysis , alkyl , metallurgy
Abstract The combination of aryl bromides, allylbenzene, base and a palladium catalyst usually results in a Heck reaction. Herein we combine these same reagents, but override the Heck pathway by employing a strong base. In the presence of LiN(SiMe 3 ) 2 , allylbenzene derivatives undergo reversible deprotonation. Transmetalation of the resulting allyllithium intermediate to LPdAr(Br) and reductive elimination provide the 1,1‐diarylprop‐2‐enes, which are not accessible by the Heck reaction. The regioselectivity in this deprotonative cross‐coupling process is catalyst‐controlled and very high.