Catalyst-Free Regioselective Diborylation of Aryllithium with Tetra(o-tolyl)diborane(4)

A catalyst-free 1,2-diborylation of aryllithium with tetra(o-tolyl)diborane(4) has been achieved, giving a series of 1,2-diborylaryl lithium species in excellent yields under mild reaction conditions, which leads to 1,2-di(tolyl)borylarenes in 60–91 % yields upon treatment with the hydride-abstracting reagent. In these transformations, one sp² C−H of arene is activated and both boryl units are utilized to build two new (sp²)C−B bonds. This represents a new strategy for selective arene diborylation. Density functional theory (DFT) calculations suggest that an aromatic nucleophilic substitution is a key step in the formation of the products. © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.