Regiocontrolled Allylic Functionalization of Internal Alkene via Selenium-pi-Acid Catalysis Guided by Boron Substitution

The selenium-pi-acid-catalysis has received increasing attention as powerful tools for olefin functionalization, but the regioselectivity is often problematic. Reported herein is a selenium-catalyzed regiocontrolled olefin transpositional chlorination and imidation reaction. The reaction outcome benefits from an allylic B(MIDA) substitution. And the stabilization of α-anion from a hemilabile B(MIDA) moiety was believed to be the key factor for selectivity. Broad substrate scope, good functional group tolerance and generally good yields were observed. The formed products were demonstrated to be valuable precursors for the synthesis a wide variety of structurally complex organoborons.