title: Ring opening of donor-acceptor cyclopropanes with the azide ion: a tool for construction of N-heterocycles.
abstract: A general method for ring opening of various donor-acceptor cyclopropanes with the azide ion through an SN 2-like reaction has been developed. This highly regioselective and stereospecific process proceeds through nucleophilic attack on the more-substituted C2 atom of a cyclopropane with complete inversion of configuration at this center. Results of DFT calculations support the SN 2 mechanism and demonstrate good qualitative correlation between the relative experimental reactivity of cyclopropanes and the calculated energy barriers. The reaction provides a straightforward approach to a variety of polyfunctional azides in up to 91 % yield. The high synthetic utility of these azides and the possibilities of their involvement in diversity-oriented synthesis were demonstrated by the developed multipath strategy of their transformations into five-, six-, and seven-membered N-heterocycles, as well as complex annulated compounds, including natural products and medicines such as (-)-nicotine and atorvastatin.
authors.affiliation: Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow, 119991 (Russia), Fax: (+7) 4959391814.
authors.forename: Konstantin L
authors.initials: KL
authors.lastname: Ivanov
authors.forename: Elena V
authors.initials: EV
authors.lastname: Villemson
authors.forename: Ekaterina M
authors.initials: EM
authors.lastname: Budynina
authors.forename: Olga A
authors.initials: OA
authors.lastname: Ivanova
authors.forename: Igor V
authors.initials: IV
authors.lastname: Trushkov
authors.forename: Mikhail Ya
authors.initials: MY
authors.lastname: Melnikov
keywords: azides; donor-acceptor systems; heterocycles; nitrogen heterocycles; nucleophilic substitution