%0 Journal Article
%A Lin, Weidong
%A Li, Weiwei
%A Lu, Dandan
%A Su, Feng
%A Wen, Ting-Bin
%A Zhang, Hui-Jun
%D 2018
%T Dual Effects of Cyclopentadienyl Ligands on Rh(III)-Catalyzed
Dehydrogenative Arylation of Electron-Rich Alkenes
%U https://acs.figshare.com/articles/journal_contribution/Dual_Effects_of_Cyclopentadienyl_Ligands_on_Rh_III_-Catalyzed_Dehydrogenative_Arylation_of_Electron-Rich_Alkenes/6911759
%R 10.1021/acscatal.8b01753.s001
%2 https://ndownloader.figshare.com/files/12634784
%K CONR
%K series styryl acetates
%K Rh
%K olefin insertion barrier
%K electron-withdrawing
%K 4 CF 3
%K electron-rich alkenes
%K aryl methyl ketones
%K olefination
%K Cp CF 3
%K C 5
%K Cp CF 3 ligand
%X Despite
extensive research on transition metal-catalyzed Fujiwara–Moritani
type C–H olefinations, the alkenes used in these transformations
are still
mainly limited to active acrylate esters and styrenes. Selective aryl
C–H
olefination with electron-rich alkenes is recognized as a challenging
issue. We herein report that simple and readily accessible electron-deficient
[CpRh(III)] and [CpCF3Rh(III)]
(CpCF3 = C5Me4CF3) complexes are powerful catalysts for dehydrogenative arylation
of electron-rich alkenes, including vinyl acetates, enamides, and
vinyl ethers. Employing an electron-withdrawing Cp or CpCF3 ligand instead of the privileged Cp* (C5Me5) ligand not only can facilitate the electrophilic
aryl C–H rhodation but also can lower the olefin insertion
barrier. Both
electron-withdrawing and electron-donating directing groups such as
-CONR2 and -NHAc could be employed in these reactions,
which
provides convenient routes toward a series styryl acetates, N-acetylindoles, and aryl methyl ketones.
%I ACS Publications