Recently the fruitful merger of organoboron chemistry and photocatalysis has come to the forefront of organic synthesis, resulting in the development of new technologies to access complex (non)borylated frameworks. Central to the success of this combination is control of boron hybridisation. Contingent on the photoactivation mode, boron as its neutral planar form or tetrahedral boronate can be used to regulate reactivity. This Minireview highlights the current state of the art in photocatalytic processes utilising organoboron compounds, paying particular attention to the role of boron hybridisation for the target transformation.

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.

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.

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.