Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides

A highly chemo-, regio-, enantio- and diastereoselective coupling of terminal alkynes, bis(pinacolato)diboron and allylic gem-dichlorides is reported. The method uses a chiral NHC−Cu catalyst which generates, in a single step, synthetically versatile chiral skipped dienes bearing a Z-alkenyl chlorid...

Descripción completa

Detalles Bibliográficos
Autores: Chaves Pouso, Andrea, Álvarez-Constantino, Andrés M., Fañanás-Mastral, Martín
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/29234
Acceso en línea:http://hdl.handle.net/10347/29234
Access Level:acceso abierto
id ES_3ee8ada65e68b4b936affbca5d68d415
oai_identifier_str oai:minerva.usc.gal:10347/29234
network_acronym_str ES
network_name_str España
repository_id_str
spelling Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-DichloridesChaves Pouso, AndreaÁlvarez-Constantino, Andrés M.Fañanás-Mastral, MartínA highly chemo-, regio-, enantio- and diastereoselective coupling of terminal alkynes, bis(pinacolato)diboron and allylic gem-dichlorides is reported. The method uses a chiral NHC−Cu catalyst which generates, in a single step, synthetically versatile chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter. Allylic gem-dichlorides are shown to be efficient substrates for catalytic asymmetric allylboration of alkynes. The method employs a chiral NHC−Cu catalyst capable of generating in a single step chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter with excellent levels of chemo-, regio- enantio- and diastereoselectivity. This high degree of functionalization makes these products versatile building blocks as illustrated with the synthesis of several optically active compounds. DFT calculations support the key presence of a metal cation bridge ligand–substrate interaction and account for the stereoselectivity outcomeWileyUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais MolecularesUniversidade de Santiago de Compostela. Departamento de Química Orgánica20222022-01-0120222022-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10347/29234reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostelainstname:Universidad de Santiago de Compostela (USC)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2020-118237RB-I00open accesshttp://purl.org/coar/access_right/c_abf2© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are madehttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:minerva.usc.gal:10347/292342026-06-15T12:47:27Z
dc.title.none.fl_str_mv Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
title Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
spellingShingle Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
Chaves Pouso, Andrea
title_short Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
title_full Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
title_fullStr Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
title_full_unstemmed Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
title_sort Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides
dc.creator.none.fl_str_mv Chaves Pouso, Andrea
Álvarez-Constantino, Andrés M.
Fañanás-Mastral, Martín
author Chaves Pouso, Andrea
author_facet Chaves Pouso, Andrea
Álvarez-Constantino, Andrés M.
Fañanás-Mastral, Martín
author_role author
author2 Álvarez-Constantino, Andrés M.
Fañanás-Mastral, Martín
author2_role author
author
dc.contributor.none.fl_str_mv Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
Universidade de Santiago de Compostela. Departamento de Química Orgánica
description A highly chemo-, regio-, enantio- and diastereoselective coupling of terminal alkynes, bis(pinacolato)diboron and allylic gem-dichlorides is reported. The method uses a chiral NHC−Cu catalyst which generates, in a single step, synthetically versatile chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter. Allylic gem-dichlorides are shown to be efficient substrates for catalytic asymmetric allylboration of alkynes. The method employs a chiral NHC−Cu catalyst capable of generating in a single step chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter with excellent levels of chemo-, regio- enantio- and diastereoselectivity. This high degree of functionalization makes these products versatile building blocks as illustrated with the synthesis of several optically active compounds. DFT calculations support the key presence of a metal cation bridge ligand–substrate interaction and account for the stereoselectivity outcome
publishDate 2022
dc.date.none.fl_str_mv 2022
2022-01-01
2022
2022-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10347/29234
url http://hdl.handle.net/10347/29234
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PID2020-118237RB-I00
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
instname:Universidad de Santiago de Compostela (USC)
instname_str Universidad de Santiago de Compostela (USC)
reponame_str Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
collection Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869406591138136064
score 15,81155

Similares en LA Referencia