title: Oxidative allene amination for the synthesis of azetidin-3-ones.
abstract: Regioselectivity in the aziridination of silyl-substituted homoallenic sulfamates is readily diverted to the distal double bond of the allene to yield endocyclic bicyclic methyleneaziridines with excellent stereocontrol. Subsequent reaction with electrophilic oxygen sources initiates facile rearrangement to densely functionalized, fused azetidin-3-ones in excellent d.r., effectively transferring the axial chirality of the allene to central chirality in the products. The steric nature of the silyl group dictates which of the two rings of the fused azetidin-3-one will undergo further functionalization, providing an additional element of diversity for the preparation of enantioenriched azetidine scaffolds with potential biological activity.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706 (USA).
authors.forename: Eileen G
authors.initials: EG
authors.lastname: Burke
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706 (USA). schomakerj@chem.wisc.edu.
authors.forename: Jennifer M
authors.initials: JM
authors.lastname: Schomaker
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis / Q000737:chemistry*; D000586:Amination; D001384:Azetidines / Q000138:chemical synthesis* / Q000737:chemistry; D001388:Aziridines / Q000138:chemical synthesis / Q000737:chemistry*; D008745:Methylation; D010084:Oxidation-Reduction
chemical_list: D000466:Alkadienes; D001384:Azetidines; D001388:Aziridines; C082735:azetidine; C025947:propadiene; C033132:aziridine
keywords: allenes; azetidin-3-ones; aziridination; heterocycles; rearrangements