Nickel-Mediated Cross-Coupling of Unactivated Neopentyl Iodides with Organozincs

Article abstract of DOI:10.1021/jo00070a022

(dppf)NiCl2 catalyzes the cross-coupling of unactivated primary neopentyl iodides with diorganozinc reagents.The zinc nucleophiles are formed by the treatment of ZnCl2*dioxane with 2 mol equiv of a Grignard reagent in an etheral solvent.The cross-coupling works optimally for diorganozincs formed from aryl chlorides or CH3MgCl.Use of aryl bromides can cause reduction and/or reductive dimerization of the electrophile.The analogous reaction with (CH3)2CuMgCl in either the presence or the absence of Group 10 metal catalysts failed to afford reasonable yields of cross-coupled products.The diorganozinc methodology overcomes many of the side reactions observed with the (dppf)NiCl2-mediated cross-coupling of Grignard reagents.