From Umpolung to Alternation: Modified Reactivity of Donor-Acceptor Cyclopropanes Towards Nucleophiles in Reaction with Nitroalkanes

Ekaterina M Budynina; Konstantin L Ivanov; Alexey O Chagarovskiy; Victor B Rybakov; Igor V Trushkov; Mikhail Ya Melnikov

doi:10.1002/chem.201504593

From Umpolung to Alternation: Modified Reactivity of Donor-Acceptor Cyclopropanes Towards Nucleophiles in Reaction with Nitroalkanes

Chemistry. 2016 Mar 7;22(11):3692-6. doi: 10.1002/chem.201504593. Epub 2016 Feb 16.

Authors

Ekaterina M Budynina¹, Konstantin L Ivanov², Alexey O Chagarovskiy^{2

3}, Victor B Rybakov², Igor V Trushkov^{2

3}, Mikhail Ya Melnikov²

Affiliations

¹ Moscow State University, Department of Chemistry, Leninskie gory, Moscow, 119991, Russian Federation. ekatbud@kinet.chem.msu.ru.
² Moscow State University, Department of Chemistry, Leninskie gory, Moscow, 119991, Russian Federation.
³ Federal Research Center of Pediatric Hematology, Oncology and Immunology, Laboratory of Chemical Synthesis, Samory Mashela, Moscow, 117997, Russian Federation.

PMID: 26880270
DOI: 10.1002/chem.201504593

Abstract

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.).

Keywords: heterocyclic compounds; nitro compounds; nucleophilic addition; pyrrolidones; small rings.

Publication types

Research Support, Non-U.S. Gov't