Nickel Nanoparticle Catalyzed Mono‐ and Di‐Reductions of <i>gem</i>‐Dibromocyclopropanes Under Mild, Aqueous Micellar Conditions
Alex B. Wood, Margery Cortes‐Clerget, Joseph R. A. Kincaid, Bhornrawin Akkachairin, Vani Singhania, Fabrice Gallou, Bruce H. Lipshutz
Abstract
Mild mono- and di-hydrodehalogenative reductions of gem-dibromocyclopropanes are described, providing an easy and green approach towards the synthesis of cyclopropanes. The methodology utilizes 0.5-5 mol % TMPhen-nickel as the catalyst, which, when activated with a hydride source such as sodium borohydride, cleanly and selectively dehalogenates dibromocyclopropanes. Double reduction proceeds in a single operation at temperatures between 20-45 °C and at atmospheric pressure in an aqueous designer surfactant medium. At lower loading and either in the absence of ligand or in the presence of 2,2'-bipyridine, this new technology can also be used to gain access to not only monobrominated cyclopropanes, interesting building blocks for further use in synthesis, but also mono- or di-deuterated analogues. Taken together, this base-metal-catalyzed process provides access to cyclopropyl-containing products and is achieved under environmentally responsible conditions.