Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis

J Am Chem Soc. 2017 Jan 25;139(3):1049-1052. doi: 10.1021/jacs.6b11336. Epub 2017 Jan 12.

Abstract

Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D2-symmetric chiral porphyrin [Co(3,5-DitBu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.

Publication types

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

MeSH terms

  • Alkenes / chemistry*
  • Azo Compounds / chemistry*
  • Catalysis
  • Cobalt / chemistry*
  • Coordination Complexes / chemistry*
  • Cyclopropanes / chemical synthesis*
  • Cyclopropanes / chemistry
  • Molecular Structure

Substances

  • Alkenes
  • Azo Compounds
  • Coordination Complexes
  • Cyclopropanes
  • Cobalt