Palladium-Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes

Angew Chem Int Ed Engl. 2024 Apr 15:e202406226. doi: 10.1002/anie.202406226. Online ahead of print.ABSTRACTIn contrast to the kinetically favored outward isomerization-hydrocarbonylation of alkenes, the disfavored inward isomerization-hydrocarbonylation of alkenes remains an important challenge. Herein, we have developed a novel and effective palladium-catalyzed inward isomerization-hydroaminocarbonylation of unactivated alkenes and aniline hydrochlorides for the formation of synthetically valuable α-aryl carboxylic amides in high yields and high site-selectivities. The high efficiency of the reaction is attributed to a relay catalysis strategy, in which the Markovnikov-favored [PdH]-PtBu3 catalyst is responsible for inward isomerization, while the [PdH]-Ruphos catalyst is responsible for hydroaminocarbonylation of the resulting conjugated aryl alkenes. The reaction exhibits highly functional group tolerance and provides a new method for formal carbonylation of remote C(sp3)-H bond.PMID:38618886 | DOI:10.1002/anie.202406226

Source: Angewandte Chemie - April 15, 2024 Category: Chemistry Authors: Xian-Jin Zou Zhao-Xing Jin Hui-Yi Yang Fei Wu Zhi-Hui Ren Zheng-Hui Guan Source Type: research