Regiocontrolled allylic functionalization of internal alkene via selenium-π-acid catalysis guided by boron substitution

The selenium-pi-acid-catalysis has received increasing attention as a powerful tool 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 alpha-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 of a wide variety of structurally complex organoborons.

Automated summary

This study presents a selenium-catalyzed regiocontrolled olefin transpositional chlorination and imidation reaction, where the use of an allylic B(MIDA) substitution improves the regioselectivity. The stabilization of alpha-anion from a hemilabile B(MIDA) moiety is believed to play a key role in the selectivity. The reaction shows broad substrate scope, good functional group tolerance, and generally good yields, making the formed products valuable precursors for the synthesis of structurally complex organoborons.