A new type of stereoselectivity in Baeyer-Villiger reactions: Access to E- and Z-olefins

Zhi Gang Zhang, Gheorghe Doru Roiban, Juan Pablo Acevedo, Iakov Polyak, Manfred T. Reetz*

*Autor correspondiente de este trabajo

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

29 Citas (Scopus)

Resumen

A new concept for accessing configurationally defined trisubstituted olefins has been developed. Starting from a common ketone precursor of the type 4-ethylidenecyclohexanone, Baeyer-Villiger monooxygenases are employed as catalysts in diastereoselective Baeyer-Villiger reactions leading to the corresponding E- or Z-configurated lactones. Wild-type cyclohexanone monooxygenase (CHMO) as catalyst delivers the E-isomers and a directed evolution mutant the opposite Z-isomers. Subsequent transition metal-catalyzed chemical transformations of a key product containing a vinyl bromide moiety provide a variety of different trisubstituted E- or Z-olefins. A model based on QM/MM sheds light on the origin of this unusual type of diastereoselectivity. In contrast to this biocatalytic approach, traditional Baeyer-Villiger reagents such as m-CPBA fail to show any selectivity, 1:1 mixtures of E- and Z-olefins being formed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Idioma originalInglés
Páginas (desde-hasta)99-106
Número de páginas8
PublicaciónAdvanced Synthesis and Catalysis
Volumen355
N.º1
DOI
EstadoPublicada - 14 ene. 2013

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