title: Synthesis of 2-chloro-2-imidoylaziridines via aza-Darzens-type reaction of 3,3-dichloro-1-azaallylic anions and N-(arylsulfonyl)imines.
abstract: 3,3-Dichloro-1-azaallylic anions, generated by deprotonation of alpha,alpha-dichloroketimines 10 with lithium diisopropylamide, reacted with N-sulfonylaldimines 7 to produce the Mannich-type products N-[2,2-dichloro-3-(N-alkylimino)-1,3-diarylpropyl]benzenesulfonamides 11. The latter stable compounds were hydrolyzed at the imino functionality to afford N-[2,2-dichloro-3-oxo-1,3-diarylpropyl]benzenesulfonamides 12 in excellent yields. N-[2,2-Dichloro-3-(N-alkylimino)-1,3-diarylpropyl]benzenesulfonamides 11 were cyclized to cis-3-aryl-2-chloro-2-imidoylaziridines 19 in 81-99% yield with high diastereoselectivity, representing a novel and readily available class of stable 2-chloroaziridines. Finally, a highly stereoselective entry to 2-(aminomethyl)-2-chloroaziridines 27 (70-98% yield; de > 95-99) was worked out from the reaction of cis-3-aryl-2-chloro-2-imidoylaziridines 19 and sodium cyanoborohydride in the presence of acetic acid. The latter 2-(aminomethyl)aziridines 27 represent stereochemically defined small azaheterocyclic rings which were scarcely reported in the literature.
authors.affiliation: Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
authors.forename: Nicola
authors.initials: N
authors.lastname: Giubellina
authors.forename: Sven
authors.initials: S
authors.lastname: Mangelinckx
authors.forename: Karl W
authors.initials: KW
authors.lastname: Törnroos
authors.forename: Norbert
authors.initials: N
authors.lastname: De Kimpe
mesh_terms: D000838:Anions / Q000737:chemistry*; D001372:Aza Compounds / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013455:Sulfur / Q000737:chemistry*
chemical_list: D000838:Anions; D001372:Aza Compounds; D001388:Aziridines; D007097:Imines; D002713:Chlorine; D013455:Sulfur