title: Radical-mediated nitrile translocation as the key step in the stereoselective transformation of 2-(4-chloro-2-cyanobutyl)aziridines to methyl cis-(1-arylmethyl-4-phenylpiperidin-2-yl)acetates.
abstract: Non-activated 2-(4-chloro-2-cyano-2-phenylbutyl)aziridines were used as building blocks for the stereoselective synthesis of novel cis-2-cyanomethyl-4-phenylpiperidines via a microwave-assisted aziridine to piperidine ring expansion followed by a radical-induced nitrile translocation through initial formation and subsequent cleavage of intermediate bicyclic iminyl radicals. Furthermore, these 2-(cyanomethyl)piperidines were shown to be eligible substrates for the preparation of methyl cis-(1-arylmethyl-4-piperidin-2-yl)acetates through a Pinner reaction using gaseous HCl in methanol.
authors.affiliation: Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
authors.forename: Karel
authors.initials: K
authors.lastname: Vervisch
authors.forename: Matthias
authors.initials: M
authors.lastname: D'hooghe
authors.forename: Karl W
authors.initials: KW
authors.lastname: Törnroos
authors.forename: Norbert
authors.initials: N
authors.lastname: De Kimpe
mesh_terms: D000085:Acetates / Q000737:chemistry*; D001388:Aziridines / Q000737:chemistry*; D008745:Methylation; D009570:Nitriles / Q000737:chemistry*; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D001388:Aziridines; D009570:Nitriles; D010880:Piperidines; C048151:4-phenylpiperidine