4.8 Article

Catalytic Radical Process for Enantioselective Amination of C(sp3)-H Bonds

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 51, Pages 16837-16841

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201808923

Keywords

amines; cobalt; heterocycles; radicals; reaction mechanisms

Funding

  1. NIH [R01-GM098777]
  2. NSF [CHE-1624216]

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A new catalytic radical system involving Co-II-based metalloradical catalysis is effective in activating sulfamoyl azides for enantioselective radical 1,6-amination of C(sp(3))-H bonds, affording six-membered chiral heterocyclic sulfamides in high yields with excellent enantioselectivities. The Co-II-catalyzed C-H amination features an unusual degree of functional-group tolerance and chemoselectivity. The unique reactivity and stereoselectivity is attributed to the underlying stepwise radical pathway. The resulting optically active cyclic sulfamides can be readily converted into synthetically useful chiral 1,3-diamine derivatives without loss in enantiopurity.

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