title: Aziridines from intramolecular alkene aziridination of sulfamates: reactivity toward carbon nucleophiles. application to the synthesis of spisulosine and its fluoro analogue.
abstract: Catalytic intramolecular alkene aziridination of sulfamate is an emerging methodology for the asymmetric synthesis of chiral functionalized amines involving the formation of bicyclic aziridines. This study demonstrates the ability of the latter to undergo ring-opening with various carbon nucleophiles: Grignard reagents, lithium salts of terminal alkynes, dithiane, malonate. These S(N)2-type reactions occur with high levels of regio- and chemoselectivity to generally afford seven-membered cyclic sulfamidates in good yields. Carbon nucleophiles have also been found to react with these sulfamidates provided that the sulfamate ester has been previously activated by introduction of a tosyl substituent on the NH group. The versatility of this strategy has been illustrated with the syntheses of spisulosine and its fluoro analogue.
authors.affiliation: Centre de Recherche de Gif-sur-Yvette, Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Malik
authors.forename: Audrey
authors.initials: A
authors.lastname: Estéoule
authors.forename: Pascal
authors.initials: P
authors.lastname: Retailleau
authors.forename: Philippe
authors.initials: P
authors.lastname: Dauban
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001388:Aziridines / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D008055:Lipids / Q000138:chemical synthesis*; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D000475:Alkenes; D001388:Aziridines; D008055:Lipids; D013451:Sulfonic Acids; D002244:Carbon; C005741:sulfamic acid; C408363:spisulosine