Photoinduced Radical Borylation of Robust Carbon–Heteroatom Bonds

Abstract Photoinduced borylation has emerged as a valuable strategy for synthesizing arylboronic esters. However, photochemical transformations involving inert bonds such as C( sp 2 )−F bonds are still challenging. Herein, we report a straightforward and operationally simple method for the activation of various inert carbon–heteroatom bonds, enabling the synthesis of diverse arylboronic esters without the need for transition metals or catalysts. Mechanistic investigations reveal that the deprotonation of DMSO plays a pivotal role in the reaction, and the excited DMSO anion can undergo electron transfer to the aryl substrates activated by anionic sp 2 – sp 3 diboron compounds, i. e., [FB 2 pin 2 ] − , thereby facilitating the cleavage of carbon–heteroatom bonds. The reaction allows the conversion of diverse C aryl –hetero bonds in batch and flow reactors into the corresponding arylboronic esters. The products can be used in a subsequent Suzuki‐Miyaura cross‐coupling without isolation.