Regioselective oxidative cleavage of conjugated dienes to access α,β-unsaturated nitriles

Abstract

A highly regioselective oxidative cleavage method has been developed for the synthesis of α,β-unsaturated nitriles from unsymmetric conjugated dienes. This transformation selectively cleaved the terminal CC double bond, providing moderate to good yields of the desired α,β-unsaturated nitriles. Notably, electron-deficient dienes exhibited superior regioselectivity over electron-rich ones. This versatile method displayed a broad substrate scope and excellent tolerance towards various functional groups. Additionally, the synthesis of N-15 atom labeled α,β-unsaturated nitriles from N-15 isotopically labeled ammonium chloride was achieved. This isotopically labeled compound is valuable for the synthesis of N-15 atom labeled rilpivirine, a well-known anti-HIV pharmaceutical.