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Diastereospecific Gold(I)‐Catalyzed Cyclization Cascade for the Controlled Preparation of N‐ and N,O‐Heterocycles
Author(s) -
Muratore Michael E.,
Konovalov Andrey I.,
ArmengolRelats Helena,
Echavarren Antonio M.
Publication year - 2018
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.201802770
Subject(s) - chemistry , cycloisomerization , oxime , enyne , catalysis , alkene , intramolecular force , carbene , moiety , cationic polymerization , medicinal chemistry , cascade , cascade reaction , diastereomer , combinatorial chemistry , stereochemistry , organic chemistry , chromatography
The reaction of oxime‐tethered 1,6‐enynes with a cationic gold(I) catalyst demonstrates a great potential for the synthesis of a range of heterocycles in a diastereospecific fashion. The control of the configuration of the oxime and the alkene of the enyne moiety is the key to selectively obtain dihydro‐1,2‐oxazines, isoxazolines or dihydropyrrole‐ N ‐oxides as single diastereoisomers. As supported by DFT calculations, these cascade reactions proceed stepwise, by the intramolecular addition of the O or N atom of the oxime onto cyclopropyl gold(I) carbene intermediates. In this study, a rare [3,3]‐sigmatropic rearrangement of nitrones is also observed.