Palladium-Catalyzed
Markovnikov Hydroaminocarbonylation
of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation
of Amides with Quaternary Carbon
posted on 2021-05-10, 20:03authored byHui-Yi Yang, Ya-Hong Yao, Ming Chen, Zhi-Hui Ren, Zheng-Hui Guan
Hydroaminocarbonylation
of alkenes is one of the most promising
yet challenging methods for the synthesis of amides. Herein, we reported
the development of a novel and effective Pd-catalyzed Markovnikov
hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted
alkenes with aniline hydrochloride salts to afford amides bearing
an α quaternary carbon. The reaction makes use of readily available
starting materials, tolerates a wide range of functional groups, and
provides a facile and straightforward approach to a diverse array
of amides bearing an α quaternary carbon. Mechanistic investigations
suggested that the reaction proceeded through a palladium hydride
pathway. The hydropalladation and CO insertion are reversible, and
the aminolysis is probably the rate-limiting step.