Premium
Nickel Nanoparticle Catalyzed Mono‐ and Di‐Reductions of gem ‐Dibromocyclopropanes Under Mild, Aqueous Micellar Conditions
Author(s) -
Wood Alex B.,
CortesClerget Margery,
Kincaid Joseph R. A.,
Akkachairin Bhornrawin,
Singhania Vani,
Gallou Fabrice,
Lipshutz Bruce H.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006162
Subject(s) - sodium borohydride , catalysis , chemistry , nickel , hydride , aqueous solution , green chemistry , pulmonary surfactant , ligand (biochemistry) , metal , inorganic chemistry , combinatorial chemistry , organic chemistry , reaction mechanism , biochemistry , receptor
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.