Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/ac...

Descripción completa

Detalles Bibliográficos
Autores: Corpas, Javier, Quirós, M. Teresa, Mauleón Pérez, Pablo, Gómez Arrayas, Ramón Jesús, Carretero Gonzálvez, Juan Carlos
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/689111
Acceso en línea:http://hdl.handle.net/10486/689111
https://dx.doi.org/10.1021/acscatal.9b02768
Access Level:acceso abierto
Palabra clave:Alkyne hydroarylation
Regioselectivity
Stereodivergence
Tandem photo/metal catalysis
Removable directing group
Photocatalytic alkene isomerization
Química
id ES_2d0e2552d6a36bd910f5a9a017519086
oai_identifier_str oai:repositorio.uam.es:10486/689111
network_acronym_str ES
network_name_str España
repository_id_str
spelling Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl AlkynesCorpas, JavierQuirós, M. TeresaMauleón Pérez, PabloGómez Arrayas, Ramón JesúsCarretero Gonzálvez, Juan CarlosAlkyne hydroarylationRegioselectivityStereodivergenceTandem photo/metal catalysisRemovable directing groupPhotocatalytic alkene isomerizationQuímicaThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acscatal.9b02768The Supporting Information (experimental procedures, spectral data, and complete DFT studies) is available (PDF) free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b02768.We report on a regioselective, stereodivergent catalytic hydroarylation of unsymmetrical dialkyl alkynes with arylboronic acids that allows highly selective access to either the E or Z diastereoisomer of trisubstituted alkenes. The E selectivity is achieved through syn-carbopalladation of the alkyne by Ar–Pd species followed by protodepalladation in which a 2-pyridyl sulfonyl (SO2Py) directing group enables complete control of the regioselectivity. Access to the complementary stereochemistry is achieved through a tandem Pd/Ir sequence, which includes hydroarylation and E→Z photoisomerization. Finally, facile removal of the directing group by reduction, Julia–Kocienski olefination, or Cu-catalyzed C(sp3)–C(sp2) or C(sp3)–C(sp3) cross coupling allows for the selective preparation of stereodefined olefins and dienesWe thank the Spanish Ministerio de Economía, Industria y Competitividad and Fondo Europeo de Desarrollo Regional (Project: CTQ2015-66954-P, MINECO/FEDER, UE) and Ministerio de Ciencia, Innovación y Universidades (Agencia Estatal de Investigación)/FEDER (Project: PGC2018-098660−B-I00) for financial support. J.C. thanks the Ministerio de Educación, Cultura y Deporte (MECD), for a FPU fellowship. M.T.Q. thanks MINECO for a Juan de la Cierva Incorporación fellowship. The Centro de Computación Científica (UAM) is acknowledged for generous allocation of computer timeAmerican Chemical SocietyDepartamento de Química OrgánicaFacultad de Ciencias20192019-11-01research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/689111https://dx.doi.org/10.1021/acscatal.9b02768reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6891112026-06-23T12:46:27Z
dc.title.none.fl_str_mv Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
title Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
spellingShingle Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
Corpas, Javier
Alkyne hydroarylation
Regioselectivity
Stereodivergence
Tandem photo/metal catalysis
Removable directing group
Photocatalytic alkene isomerization
Química
title_short Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
title_full Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
title_fullStr Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
title_full_unstemmed Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
title_sort Metal- and Photocatalysis To Gain Regiocontrol and Stereodivergence in Hydroarylations of Unsymmetrical Dialkyl Alkynes
dc.creator.none.fl_str_mv Corpas, Javier
Quirós, M. Teresa
Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author Corpas, Javier
author_facet Corpas, Javier
Quirós, M. Teresa
Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author_role author
author2 Quirós, M. Teresa
Mauleón Pérez, Pablo
Gómez Arrayas, Ramón Jesús
Carretero Gonzálvez, Juan Carlos
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Alkyne hydroarylation
Regioselectivity
Stereodivergence
Tandem photo/metal catalysis
Removable directing group
Photocatalytic alkene isomerization
Química
topic Alkyne hydroarylation
Regioselectivity
Stereodivergence
Tandem photo/metal catalysis
Removable directing group
Photocatalytic alkene isomerization
Química
description This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acscatal.9b02768
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-11-01
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/689111
https://dx.doi.org/10.1021/acscatal.9b02768
url http://hdl.handle.net/10486/689111
https://dx.doi.org/10.1021/acscatal.9b02768
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
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
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869405284417404928
score 15,301629

Similares en LA Referencia