Enantioselective Radical Construction of 5-Membered Cyclic Sulfonamides by Metalloradical C-H Amination

J Am Chem Soc. 2019 Nov 13;141(45):18160-18169. doi: 10.1021/jacs.9b08894. Epub 2019 Nov 1.

Abstract

Both arylsulfonyl and alkylsulfonyl azides can be effectively activated by the cobalt(II) complexes of D2-symmetric chiral amidoporphyrins for enantioselective radical 1,5-C-H amination to stereoselectively construct 5-membered cyclic sulfonamides. In addition to C-H bonds with varied electronic properties, the Co(II)-based metalloradical system features chemoselective amination of allylic C-H bonds and is compatible with heteroaryl groups, producing functionalized 5-membered chiral cyclic sulfonamides in high yields with high enantioselectivities. The unique profile of reactivity and selectivity of the Co(II)-catalyzed C-H amination is attributed to its underlying stepwise radical mechanism, which is supported by several lines of experimental evidence.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Amination
  • Azides / chemistry
  • Catalysis
  • Cobalt / chemistry
  • Coordination Complexes / chemistry
  • Cyclic S-Oxides / chemical synthesis*
  • Stereoisomerism
  • Sulfonamides / chemical synthesis*

Substances

  • Azides
  • Coordination Complexes
  • Cyclic S-Oxides
  • Sulfonamides
  • Cobalt