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The B-alkylpinacolboranes are easy to handle since they are moisture- and air-stable. The generation of radicals from B-alkylpinacolboranes requires formation of ate complex followed by treatment with a strong oxidant. We report here that B-alkylpinacolboranes can be used as radical precursors in the absence of oxidizing agent, using in situ transesterification process. Highly efficient chain reactions, leading to the products of allylation, bromination as well as hydrogen atom transfer, are reported.