Welcome to radical catalysis: Radicals are “tamed” in transition-metal complexes which serve as catalysts for a number of reactions—Kumada couplings (see scheme), highly regioselective cobalt-catalyzed eliminations, Markovnikov additions, and reductive epoxide openings catalyzed by a titanium/rhodium system. All of these reactions are powered by the high reactivity of radical intermediates in the catalytic cycle of the metal-catalyzed process.
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Ford et al. (2009) studied this question.
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