Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes

Autores
Grayson, Matthew N.; Pellegrinet, Silvina Carla; Goodman, Jonathan M.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
BINOL-derived phosphoric acids catalyze the asymmetric allylboration of aldehydes. DFT and QM/MM hybrid calculations showed that the reaction proceeds via a transition state involving both a hydrogen-bonding interaction from the catalyst hydroxyl group to the pseudoaxial oxygen of the cyclic boronate and a stabilizing interaction from the phosphoryl oxygen of the catalyst to the formyl hydrogen of the aldehyde. These interactions lower the energy of the transition structure and provide extra rigidity to the system. This mechanistic pathway is consistent with the experimentally observed  enantioselectivity  except in one case. We have used our model’s predictions to guide our own experimental work. The conflict is resolved in favor of our calculations.
Fil: Grayson, Matthew N.. University of Cambridge; Reino Unido
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Goodman, Jonathan M.. University of Cambridge; Reino Unido
Materia
BINOL-DERIVED PHOSPHORIC ACID
ASYMMETRIC ALLYLBORATION
CATALYSIS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/107959
Acceder
id CONICETDig_6f8ffb26160f0226f84b2cb17d3a8fba
oai_identifier_str oai:ri.conicet.gov.ar:11336/107959
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydesGrayson, Matthew N.Pellegrinet, Silvina CarlaGoodman, Jonathan M.BINOL-DERIVED PHOSPHORIC ACIDASYMMETRIC ALLYLBORATIONCATALYSIShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1BINOL-derived phosphoric acids catalyze the asymmetric allylboration of aldehydes. DFT and QM/MM hybrid calculations showed that the reaction proceeds via a transition state involving both a hydrogen-bonding interaction from the catalyst hydroxyl group to the pseudoaxial oxygen of the cyclic boronate and a stabilizing interaction from the phosphoryl oxygen of the catalyst to the formyl hydrogen of the aldehyde. These interactions lower the energy of the transition structure and provide extra rigidity to the system. This mechanistic pathway is consistent with the experimentally observed  enantioselectivity  except in one case. We have used our model’s predictions to guide our own experimental work. The conflict is resolved in favor of our calculations.Fil: Grayson, Matthew N.. University of Cambridge; Reino UnidoFil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Goodman, Jonathan M.. University of Cambridge; Reino UnidoAmerican Chemical Society2012-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/107959Grayson, Matthew N.; Pellegrinet, Silvina Carla; Goodman, Jonathan M.; Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes; American Chemical Society; Journal of the American Chemical Society; 134; 5; 1-2012; 2716-27220002-7863CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ja210200dinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ja210200dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:45:04Zoai:ri.conicet.gov.ar:11336/107959instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:45:05.05CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
title Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
spellingShingle Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
Grayson, Matthew N.
BINOL-DERIVED PHOSPHORIC ACID
ASYMMETRIC ALLYLBORATION
CATALYSIS
title_short Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
title_full Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
title_fullStr Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
title_full_unstemmed Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
title_sort Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
dc.creator.none.fl_str_mv Grayson, Matthew N.
Pellegrinet, Silvina Carla
Goodman, Jonathan M.
author Grayson, Matthew N.
author_facet Grayson, Matthew N.
Pellegrinet, Silvina Carla
Goodman, Jonathan M.
author_role author
author2 Pellegrinet, Silvina Carla
Goodman, Jonathan M.
author2_role author
author
dc.subject.none.fl_str_mv BINOL-DERIVED PHOSPHORIC ACID
ASYMMETRIC ALLYLBORATION
CATALYSIS
topic BINOL-DERIVED PHOSPHORIC ACID
ASYMMETRIC ALLYLBORATION
CATALYSIS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv BINOL-derived phosphoric acids catalyze the asymmetric allylboration of aldehydes. DFT and QM/MM hybrid calculations showed that the reaction proceeds via a transition state involving both a hydrogen-bonding interaction from the catalyst hydroxyl group to the pseudoaxial oxygen of the cyclic boronate and a stabilizing interaction from the phosphoryl oxygen of the catalyst to the formyl hydrogen of the aldehyde. These interactions lower the energy of the transition structure and provide extra rigidity to the system. This mechanistic pathway is consistent with the experimentally observed  enantioselectivity  except in one case. We have used our model’s predictions to guide our own experimental work. The conflict is resolved in favor of our calculations.
Fil: Grayson, Matthew N.. University of Cambridge; Reino Unido
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Goodman, Jonathan M.. University of Cambridge; Reino Unido
description BINOL-derived phosphoric acids catalyze the asymmetric allylboration of aldehydes. DFT and QM/MM hybrid calculations showed that the reaction proceeds via a transition state involving both a hydrogen-bonding interaction from the catalyst hydroxyl group to the pseudoaxial oxygen of the cyclic boronate and a stabilizing interaction from the phosphoryl oxygen of the catalyst to the formyl hydrogen of the aldehyde. These interactions lower the energy of the transition structure and provide extra rigidity to the system. This mechanistic pathway is consistent with the experimentally observed  enantioselectivity  except in one case. We have used our model’s predictions to guide our own experimental work. The conflict is resolved in favor of our calculations.
publishDate 2012
dc.date.none.fl_str_mv 2012-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/107959
Grayson, Matthew N.; Pellegrinet, Silvina Carla; Goodman, Jonathan M.; Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes; American Chemical Society; Journal of the American Chemical Society; 134; 5; 1-2012; 2716-2722
0002-7863
CONICET Digital
CONICET
url http://hdl.handle.net/11336/107959
identifier_str_mv Grayson, Matthew N.; Pellegrinet, Silvina Carla; Goodman, Jonathan M.; Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes; American Chemical Society; Journal of the American Chemical Society; 134; 5; 1-2012; 2716-2722
0002-7863
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ja210200d
info:eu-repo/semantics/altIdentifier/doi/10.1021/ja210200d
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
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:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1844614489624805376
score 13.070432

Publicaciones similares