Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji-Trost Homologative Amination Reaction toward Allylic Amines

A visible light-induced palladium-catalyzed homologativethree-componentsynthesis of allylic amines has been developed. This protocol proceeds via a unique mechanism involving two distinct cycles enabledby the same Pd(0) catalyst: a visible light-induced hybrid radicalalkyl Heck reaction between 1,1-dielectrophile and styrene, followedby the in dark classical Tsuji-Trost-type allylicsubstitution reaction. This method works well with a broad range ofprimary and secondary amines, aryl alkenes, dielectrophiles, and incomplex settings. The regiochemistry of the obtained products is primarilygoverned by the structure of 1,1-dielectrophile. Involvement of & pi;-allylpalladium intermediates allowed for the control of stereoselectivity,which has been demonstrated with up to 95:5 er.

Automated summary

A visible light-induced palladium-catalyzed synthesis of allylic amines was developed. This method involves a hybrid radical alkyl Heck reaction and a classical Tsuji-Trost-type allylic substitution reaction, enabled by the same Pd(0) catalyst through two distinct cycles. It shows good compatibility with various primary and secondary amines, aryl alkenes, dielectrophiles, and complex settings, and the regiochemistry of the products is controlled by the structure of 1,1-dielectrophile. The stereoselectivity can be controlled by the involvement of π-allylpalladium intermediates, achieving up to 95:5 er.