Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds

J Am Chem Soc. 2012 Jun 27;134(25):10693-7. doi: 10.1021/ja304068t. Epub 2012 Jun 6.


Through the use of a catalyst formed in situ from NiBr(2)·diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C-C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as -10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C-C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C-B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Boron / chemistry*
  • Carbon / chemistry*
  • Catalysis
  • Electrochemistry
  • Halogens / chemistry*
  • Molecular Structure
  • Nickel / chemistry*
  • Organic Chemicals / chemistry*


  • Halogens
  • Organic Chemicals
  • Carbon
  • Nickel
  • Boron