Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
- Barluenga, J. 1
- Rodríguez, F. 1
- Vadecard, J. 1
- Bendix, M. 1
- Fañanas, F.J. 1
- López-Ortiz, F. 2
- Rodríguez, M.A. 3
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1
Universidad de Oviedo
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2
Universidad de Almería
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3
Universidad de La Rioja
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ISSN: 0002-7863
Año de publicación: 1999
Volumen: 121
Número: 38
Páginas: 8776-8782
Tipo: Artículo
beta Ver similares en nube de resultadosOtras publicaciones en: Journal of the American Chemical Society
Resumen
In-situ-generated dialkylboroxy and diaminoboroxy Fischer carbene complexes lead to oxaborolane or oxazaborolidine derivatives via an intramolecular C-H insertion reaction. Further oxidation of these intermediates yields 1,3-diol or 1,2-amino alcohol derivatives. Diastereoselectivities as high as 99% are reached when starting from boroxy Fischer carbene complexes derived from terpenes, which represents a regio- and diastereoselective modification of this type of natural product. The influence of the C(β) substituents relative to the boron atom on the reaction path is studied, and a mechanism is proposed after identification of an intermediate by NMR. In addition, theoretical calculations show the presence of a boron-metal interaction, which could result as key step to the C-H insertion reaction.