Pd/Mengphos-Catalyzed High-Order [4+4] Cycloaddition for Efficient Synthesis of Oxazocines

Abstract

AbstractThe development of new catalytic systems that enable regio- and chemoselective construction of diversely functionalized oxazocines is an important topic in organic synthesis and pharmacochemistry. Herein, a novel Pd/Mengphos complex was designed and applied in a palladium-catalyzed high-order [4+4] cycloaddition of 2-substituted allylic carbonates to α,β-unsaturated imines, allowing facile access to versatile oxazocines in good yields with excellent b/l and Z/E selectivities (up to 92% yield and complete b/l and Z/E selectivities). The reaction exhibited a broad substrate scope, mild reaction conditions, and good functional group compatibility. In addition, an asymmetric version has also been tested, affording the desired oxazocines in moderate to good enantioselectivity.