title: Diastereo- and regioselective addition of thioamide dianions to imines and aziridines: synthesis of N-thioacyl-1,2-diamines and N-thioacyl-1,3-diamines.
abstract: Addition reactions of thioamide dianions that were derived from N-arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N-thioacyl-1,2-diamines in a highly diastereoselective manner in good-to-excellent yields. The diastereomeric purity of these N-thioacyl-1,2-diamines could be enriched by simple recrystallization. The reduction of N-thioacyl-1,2-diamines with LiAlH(4) gave their corresponding 1,2-diamines in moderate-to-good yields with retention of their stereochemistry. The oxidative-desulfurization/cyclization of an N-thioacyl-1,2-diamine in CuCl(2)/O(2) and I(2)/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N-tosylaziridines gave the addition products of N-thioacyl-1,3-diamines with low diastereoselectivity but high regioselectivity and in good-to-excellent yields. The use of AlMe(3) as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X-ray diffraction.
authors.affiliation: Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan. fshiba@gifu-u.ac.jp
authors.forename: Fumitoshi
authors.initials: F
authors.lastname: Shibahara
authors.forename: Shun-ichiro
authors.initials: S
authors.lastname: Kobayashi
authors.forename: Toshifumi
authors.initials: T
authors.lastname: Maruyama
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Murai
mesh_terms: D000577:Amides / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D001388:Aziridines / Q000737:chemistry*; D003959:Diamines / Q000138:chemical synthesis* / Q000737:chemistry; D007097:Imines / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000577:Amides; D000838:Anions; D001388:Aziridines; D003959:Diamines; D007097:Imines; D013438:Sulfhydryl Compounds