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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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
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spelling Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of TerpenesBarluenga, 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]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.1999info:eu-repo/semantics/articleSubtype: Articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://investigacion.unirioja.es/documentos/5bbc68e3b750603269e8115freponame:RIUR. Repositorio Institucional de la Universidad de La Riojainstname:Universidad de La Rioja (UR)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/JA991161+info:eu-repo/semantics/altIdentifier/wos/WOS:000083032500013info:eu-repo/semantics/altIdentifier/pissn/0002-7863Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes, 1999, vol. 121, núm. 38, pág. 8776-8782info:eu-repo/semantics/openAccessoai:portal.dialnet.es:doc/5bbc68e3b750603269e8115f2026-06-14T12:47:17Z
dc.title.none.fl_str_mv Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
title Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
spellingShingle Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
Barluenga, J. [0000-0002-6474-7782]
title_short Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
title_full Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
title_fullStr Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
title_full_unstemmed Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
title_sort Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes
dc.creator.none.fl_str_mv 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]
author Barluenga, J. [0000-0002-6474-7782]
author_facet 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]
author_role author
author2 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]
author2_role author
author
author
author
author
author
description 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.
publishDate 1999
dc.date.none.fl_str_mv 1999
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Subtype: Article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://investigacion.unirioja.es/documentos/5bbc68e3b750603269e8115f
url https://investigacion.unirioja.es/documentos/5bbc68e3b750603269e8115f
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/JA991161+
info:eu-repo/semantics/altIdentifier/wos/WOS:000083032500013
info:eu-repo/semantics/altIdentifier/pissn/0002-7863
Intramolecular C-H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio and Diastereoselective Modification of Terpenes, 1999, vol. 121, núm. 38, pág. 8776-8782
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:RIUR. Repositorio Institucional de la Universidad de La Rioja
instname:Universidad de La Rioja (UR)
instname_str Universidad de La Rioja (UR)
reponame_str RIUR. Repositorio Institucional de la Universidad de La Rioja
collection RIUR. Repositorio Institucional de la Universidad de La Rioja
repository.name.fl_str_mv
repository.mail.fl_str_mv
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