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From Umpolung to Alternation: Modified Reactivity of Donor–Acceptor Cyclopropanes Towards Nucleophiles in Reaction with Nitroalkanes
Author(s) -
Budynina Ekaterina M.,
Ivanov Konstantin L.,
Chagarovskiy Alexey O.,
Rybakov Victor B.,
Trushkov Igor V.,
Melnikov Mikhail Ya.
Publication year - 2016
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.201504593
Subject(s) - cyclopropane , nucleophile , umpolung , reactivity (psychology) , chemistry , acceptor , cleavage (geology) , ring (chemistry) , medicinal chemistry , stereochemistry , organic chemistry , catalysis , materials science , medicine , physics , alternative medicine , pathology , fracture (geology) , composite material , condensed matter physics
A conceptually new type of donor–acceptor cyclopropane reactivity towards nucleophiles has been disclosed. An essential characteristic of the process is an unusual nucleophilic attack on the C(3)‐position of a cyclopropane, combined with typical small ring‐opening by cleavage of the C(1)−C(2) bond between the acceptor and the donor. Based on this new reaction between cyclopropane‐1,1‐diesters and nitroalkanes, we developed a convenient approach to γ‐nitroesters that can be efficiently transformed to the substituted pyrrolidones, structural analogues of racetame family drugs (rolipram, phenylpiracetam, etc.).

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