title: Rhodium(III)-Catalyzed Allylic C(sp(3))-H Activation of Alkenyl Sulfonamides: Unexpected Formation of Azabicycles.
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.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO 80523 (USA) http://sites.chem.colostate.edu/rovislab.
authors.forename: Alexis
authors.initials: A
authors.lastname: Archambeau
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO 80523 (USA) http://sites.chem.colostate.edu/rovislab. rovis@colostate.edu.
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D053961:Azabicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D053961:Azabicyclo Compounds; D009942:Organometallic Compounds; D013449:Sulfonamides; D012238:Rhodium
keywords: 1,3-migration; 4π-electrocyclization; CH insertion; azabicycles; rhodium