Rhodium(III)-Catalyzed Allylic C(sp(3))-H Activation of Alkenyl Sulfonamides: Unexpected Formation of Azabicycles

Angew Chem Int Ed Engl. 2015 Nov 2;54(45):13337-40. doi: 10.1002/anie.201504150. Epub 2015 Sep 11.

Abstract

Unsaturated N-sulfonamides undergo a Rh(III)-catalyzed allylic C(sp(3))-H activation followed by insertion with an exogenous internal alkyne. The reaction generates [3.3.0], [4.3.0], and [5.3.0] azabicyclic structures with excellent diastereoselectivity. Deuterium labeling experiments implicate a 1,3-Rh shift as a key step in the mechanism.

Keywords: 1,3-migration; 4π-electrocyclization; CH insertion; azabicycles; rhodium.

Publication types

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

MeSH terms

  • Alkenes / chemistry
  • Alkynes / chemistry*
  • Azabicyclo Compounds / chemical synthesis*
  • Azabicyclo Compounds / chemistry
  • Catalysis
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Rhodium / chemistry*
  • Sulfonamides / chemistry*

Substances

  • Alkenes
  • Alkynes
  • Azabicyclo Compounds
  • Organometallic Compounds
  • Sulfonamides
  • Rhodium