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3,3‐Sigmatropic Rearrangements Involving N−O Bond‐Cleavage of Enehydroxylamine Derivatives
Author(s) -
Reis Lucinda V.,
Lobo Ana M.,
Prabhakar Sundaresan,
Duarte Mariana P.
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200301)2003:1<190::aid-ejoc190>3.0.co;2-w
Subject(s) - chemistry , sigmatropic reaction , electrophile , intramolecular force , sodium hydride , hydride , medicinal chemistry , deuterium , cleavage (geology) , bond cleavage , stereochemistry , organic chemistry , hydrogen , physics , geotechnical engineering , quantum mechanics , fracture (geology) , engineering , catalysis
Enehydroxylamines, derived from carbocyclic and heterocyclic 1,3‐dioxo compounds, react with a variety of unsaturated electrophiles to give, in good to excellent yields, substances that in general undergo 3,3‐sigmatropic rearrangements either spontaneously or upon heating. In those cases in which such reactions failed, addition of sodium hydride was found to induce the transformation. A study of the rearrangement by use of deuterium‐labelled compounds showed that no crossover occurs, indicating the intramolecular nature of the process. The method provides 2,3‐ or 3,4‐disubstituted cyclohexenones, 5,6‐disubstituted barbiturates and the corresponding fused pyrrole and imidazolinone derivatives. (© Wiley‐VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2003)