Catalyst‐Free Diborylation and Silaboration of Azoarenes: A Simple Photoinduced Approach

Abstract The diborylation of the N=N double bond of azoarenes has been achieved using a commercially available diboron reagent, B 2 cat 2 [bis(catecholato)diboron]. By utilizing the photo‐switchable nature of azoarenes under blue‐LED light irradiation, an uncatalyzed diborylation and silaboration yielded a broad range of functionalized hydrazine derivatives. The mechanistic origin validates the importance of cis configuration, which is corroborated by theoretical calculations.