Comparing and taming the reactivity of HWE and Wittig reagents with cyclic hemiacetals

A practical solution to the formation of mixtures of E/Z and open/cyclic isomers in the reaction of (2R,4S)-4-hydroxy-2-methylpentanal (as its hemiacetal, a lactol) with conjugated phosphoranes (stabilised Wittig reagents) and Horner-Wadsworth-Emmons reagents is disclosed. The HWE reaction has a str...

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Detalles Bibliográficos
Autores: Carrillo Arregui, Jokin, Costa i Arnau, Anna M., Sidera Portela, Mireia, Vilarrasa i Llorens, Jaume
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2011
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/45524
Acceso en línea:https://hdl.handle.net/2445/45524
Access Level:acceso abierto
Palabra clave:Química orgànica
Reactivitat (Química)
Nomenclatura química
Síntesi orgànica
Organic chemistry
Reactivity (Chemistry)
Chemical nomenclature
Organic synthesis
Descripción
Sumario:A practical solution to the formation of mixtures of E/Z and open/cyclic isomers in the reaction of (2R,4S)-4-hydroxy-2-methylpentanal (as its hemiacetal, a lactol) with conjugated phosphoranes (stabilised Wittig reagents) and Horner-Wadsworth-Emmons reagents is disclosed. The HWE reaction has a strong bias to give oxolanes. On the other hand, stabilised Wittig reagents give unsaturated carboxyl derivatives of configuration E (major) and oxolanes (minor); the latter can be avoided by addition of CF3CH2OH or using morpholine amide phosphorane.