Carbon-centered radicals have traditionally been generated from the reaction of alkyl halides with trialkyltin hydrides. Unfortunately the resultant trialkyltin byproducts are toxic, prohibiting the use of radical chemistry on an industrial scale. Furthermore, trialkyltin hydrides must be used stoichiometrically, so one equivalent of Bu3SnX is generated per equivalent of hydrogen atoms. The generation of radicals from alkyl halides requires electron transfer. A hydride complex that can serve as a source of electrons is [CpV(CO)3H]–, reported by Kinney, Jones, and Bergman in 1981. It can be regenerated from H2 in the presence of base, and thus can serve as a catalytic replacement for trialkyltin hydrides in the initiation of radical cyclizations.

Radical cyclizations catalyzed by [NEt4][CpV(CO)3H]

255th National Meeting (2018)

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