title: Nickel-catalyzed carbon-carbon bond-forming reactions of unactivated tertiary alkyl halides: Suzuki arylations.
abstract: The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr(2)·diglyme/4,4'-di-tert-butyl-2,2'-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C-C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Susan L
authors.initials: SL
authors.lastname: Zultanski
authors.forename: Gregory C
authors.initials: GC
authors.lastname: Fu
mesh_terms: D001713:Biphenyl Compounds / Q000737:chemistry; D001965:Bromides / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D008697:Methane / Q000737:chemistry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*
chemical_list: D001713:Biphenyl Compounds; D001965:Bromides; D002244:Carbon; D008697:Methane; D009532:Nickel; C010574:biphenyl