Unsymmetrical 1,1-diborated multisubstituted sp(3)-carbons formed via a metal-free concerted-asynchronous mechanism

Ana B. Cuenca, Jessica Cid, Diego García-López, Jorge J. Carbó, Elena Fernández

Research output: Indexed journal article Articlepeer-review

63 Citations (Scopus)

Abstract

We have experimentally proved the unsymmetrical 1,1-diboration of diazo compounds, formed in situ from aldehydes and cyclic and non-cyclic ketones, in the absence of any transition metal complex. The heterolytic cleavage of the mixed diboron reagent, Bpin-Bdan, and the formation of two geminal C-Bpin and C-Bdan bonds has been rationalised based on DFT calculations to occur via a concerted-asynchronous mechanism. Diastereoselection is attained on substituted cyclohexanones and DFT studies provide understanding on the origin of the selectivity. The alkoxide-assisted selective deborylation of Bpin from multisubstituted sp3-carbon and generation of a Bdan stabilized carbanion, easily conducts a selective protodeboronation sequence.

Original languageEnglish
Pages (from-to)9659-9664
Number of pages6
JournalOrganic and Biomolecular Chemistry
Volume13
Issue number37
DOIs
Publication statusPublished - 29 Jul 2015
Externally publishedYes

Keywords

  • Gem-dimetallic compounds
  • Tertiary boronic esters
  • Asymmetric-synthesis
  • Hydroboration
  • Diborylation
  • Insertion
  • Diborylmethane
  • Construction
  • Derivatives
  • Cyclopropyl

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