Zhengyang Gao, Kuan Zhang, Wentao Zhang, Xin-Hua Duan, Li‐Na Guo
An efficient synthesis of densely functionalized azetidines has been achieved via a Ni-catalyzed 1,4-alkylarylation of 1,3-enynes using 1-azabicyclo[1.1.0]butanes (ABBs) and arylboronic acids. This three-component reaction offers an easy way to incorporate an allene fragment into azetidines. The method is characterized by a broad substrate scope and excellent functional group compatibility. Mechanistic studies have revealed a polar-radical relay mechanism for this transformation.