Reactivity of a-Oxophosphonium Ylides A Contribution to the Mechanistics 英文参考文献.docVIP

Molecules 1999, 4, 219-231 molecules ISSN 1420-3049 Reactivity of a -Oxophosphonium Ylides: A Contribution to the Mechanistics Teresa M.V.D. Pinho e Melo*, António M. d’A. Rocha Gonsalves, Sara M. S. Carrapato and Ana M. O. M. P. Taborda Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, 3000 Coimbra, Portugal Tel.: (351) 39 852080, Fax: (351) 39 826068, E-mail: tmelo@cygnus.ci.uc.pt *Author to whom correspondence should be addressed. Received: 9 June 1999 / Accepted: 29 June 1999 / Published: 17 July 1999 Abstract: Ylides 1f and 1g react with chlorine, with bromine and with N-chlorosuccinimide in the presence of a range of nucleophiles. The 2,3-disubstitutedbutenedioates obtained in this way allow us to gather more information about the mechanism involved. Ylide 1c was also studied showing similar reactivity and leading to the highly selective synthesis of 2,3- disubstituted-3-phenylpropenoates. Keywords: phosphorus ylides, tetrasubstituted alkenes. Introduction We have previously studied the reactivity of diethyl 2-oxo-3-triphenylphosphoranylidene- butanedioate 1a with chlorine and bromine in the presence of a range of nucleophiles [1]. Triphenylphosphine oxide was eliminated and 2,3-disubstituted diethyl butenedioates were formed (Scheme 1). The reaction of N-bromosuccinimide and N-chlorosuccinimide in methanol also gave 2,3- disubstituted diethylbutenedioates. Several of the reactions were highly stereoselective whereas others gave both (E) and (Z) isomers. The method offers a route to some simple tetrasubstituted alkenes of a type that was poorly represented in the literature. ? 1999 by the authors. Reproduction of this article, by any means, is permitted for noncommercial purposes.  220 Molecules 1999, 4 O O Y X EtO2C Y X XY EtO and / or OEt - OPPh3 EtO2C CO2Et CO2Et O PPh3 1a Scheme 1. The formation of the observed products was explained by postula