Synergistic Organoboron/Palladium Catalysis for Regioselective N-Allylations of Azoles with Allylic Alcohols

A method for regioselective palladium-catalyzed allylic alkylation of ambident nitrogen heterocycles, employing simple allylic alcohols as electrophile precursors, is described. An organoboron co-catalyst serves both to activate the azole-type nucleophile toward selective N-functionalization and to accelerate the formation of a pi-allylpalladium complex from the allylic alcohol. The method can be applied to various heterocycle types, including 1,2,3-and 1,2,4-triazoles, tetrazoles, pyrazoles, and purines, and can be extended to substituted allylic alcohol partners.

Automated summary

A regioselective palladium-catalyzed allylic alkylation method using simple allylic alcohols as electrophile precursors is developed. An organoboron co-catalyst is used to activate the azole-type nucleophile and accelerate the formation of a pi-allylpalladium complex from the allylic alcohol. The method can be applied to various heterocycle types.