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Ring Opening of Donor–Acceptor Cyclopropanes with the Azide Ion: A Tool for Construction of N‐Heterocycles
Author(s) -
Ivanov Konstantin L.,
Villemson Elena V.,
Budynina Ekaterina M.,
Ivanova Olga A.,
Trushkov Igor V.,
Melnikov Mikhail Ya.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405551
Subject(s) - azide , ring (chemistry) , ion , acceptor , chemistry , combinatorial chemistry , stereochemistry , organic chemistry , physics , condensed matter physics
A general method for ring opening of various donor–acceptor cyclopropanes with the azide ion through an S N 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 S N 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.