Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes

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...

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Detalles Bibliográficos
Autores: Barluenga, J. [0000-0002-6474-7782], Rodríguez, F., Vadecard, J., Bendix, M., Fañanas, F.J. [0000-0003-1947-9851], López-Ortiz, F. [0000-0003-1786-0157], Rodríguez, M.A. [0000-0003-0123-9905]
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:1999
País:España
Institución:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc68e3b750603269e8115f
Acceso en línea:https://investigacion.unirioja.es/documentos/5bbc68e3b750603269e8115f
Access Level:acceso abierto
Descripción
Sumario: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.