MIMIRC Reactions of nitromethane with electrophilic alkenes in solvent-free reactions under microwave irradiation

New highly functionalized cyclohexenes 3a– h or 4a– i (after demethoxycarbonylation or deamidation at C-3) are obtained from the reaction of nitromethane 1 with electrophilic alkenes 2a– i RCH=C(CN)(Y) with Y=CO 2R′, CN, CONH 2 in a solvent-free reaction catalyzed by piperidine at room temperature o...

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Bibliographic Details
Published in:Tetrahedron 2002-07, Vol.58 (29), p.5865-5875
Main Authors: Michaud, David, Hamelin, Jack, Texier-Boullet, Françoise, Toupet, Loı̈c
Format: Article
Language:English
Subjects:
cyclohexenes
electrophilic alkenes
Michael additions
microwave heating
nitrocompounds
solvent-free reactions
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Summary:New highly functionalized cyclohexenes 3a– h or 4a– i (after demethoxycarbonylation or deamidation at C-3) are obtained from the reaction of nitromethane 1 with electrophilic alkenes 2a– i RCH=C(CN)(Y) with Y=CO 2R′, CN, CONH 2 in a solvent-free reaction catalyzed by piperidine at room temperature or under focused microwave irradiation after a few min. The mechanism involves a double Michael addition followed by intramolecular ring closure (MIMIRC reaction). The reaction is diastereoselective (two diastereoisomers only). In some cases, non-cyclized intermediates have been isolated. Stœchiometric amounts of piperidine promote the demethoxycarbonylation of 3 . When Y is an amide group, a first example of chemical deamidation is observed. Graphic
ISSN:0040-4020
1464-5416
DOI:10.1016/S0040-4020(02)00568-9