Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters**

Abstract

Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in organic synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C−B bonds, α‐boryl radicals have recently reemerged as versatile open‐shell alternatives to access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent on photo‐ or transition metal‐catalysis activation to efficiently generate radical species. Here, we disclose a facile activation of α‐halo boronic esters using only visible light and a simple Lewis base to enable homolytic scission. Intermolecular addition to styrenes facilitates the rapid construction of highly versatile E‐allylic boronic esters. The simplicity of activation permits the strategic merger of this construct with selective energy transfer catalysis to enable the complimentary stereodivergent synthesis of Z‐allylic boronic esters.