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Updated: Jan 20, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Hydrogen Atom Transfer Induced Boron Retaining Coupling of Organoboronic Esters and Organolithium Reagents
Dinghai Wang1, Christian Mück-Lichtenfeld1, Armido Studer1
1Organisch-Chemisches Institut , Westfälische Wilhelms-Universität , Corrensstraße 40 , 48149 Münster , Germany.
Abstract:
α-Functionalization of alkyl boronic esters and homologation of aryl boronic esters by regioselective radical C(sp)-H activation in boron-ate complexes is reported. Reaction of commercial or readily accessed aryl boronic acid pinacol esters with alkyl lithium reagents provides boron-ate complexes. Selective α-C-H abstraction by in situ generated trifluoromethyl radicals leads to radical anions that undergo electron transfer oxidation followed by 1,2-aryl/alkyl migration from boron to carbon to give the α-arylated/alkylated alkyl boronic esters. The valuable boronic ester functionality remains in the products and the cheap trifluoromethyl iodide acts as the oxidant in these C-C couplings. The 1,2-alkyl migration from boron to carbon is highly stereospecific allowing access to stereoisomerically pure boronic esters.
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