The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation
The Michael addition of activated methylenes to β-substituted α,β-unsaturated aldehydes (enals) via iminium catalysis takes place following reactivity and enantioselectivity patterns which depend on the electronic nature of the substituent in the β position (β-aryl or β-alkyl). Application of the sa...
| Autores: | , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/681765 |
| Acceso en línea: | http://hdl.handle.net/10486/681765 https://dx.doi.org/10.1021/acscatal.7b02806 |
| Access Level: | acceso abierto |
| Palabra clave: | Acidity Asymmetric organocatalysis Enals Iminium activation Michael addition Química |
| id |
ES_c56c39dd33dbef1e97a56ff83c11ec68 |
|---|---|
| oai_identifier_str |
oai:repositorio.uam.es:10486/681765 |
| network_acronym_str |
ES |
| network_name_str |
España |
| repository_id_str |
|
| spelling |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium ActivationDuce, SaraAlonso Montero, María InésLamsabhi, Al MokhtarRodrigo, EduardoMorales, SaraGarcía Ruano, José LuisPoveda, AnaMauleón Pérez, PabloCid de la Plata, María BelénAcidityAsymmetric organocatalysisEnalsIminium activationMichael additionQuímicaThe Michael addition of activated methylenes to β-substituted α,β-unsaturated aldehydes (enals) via iminium catalysis takes place following reactivity and enantioselectivity patterns which depend on the electronic nature of the substituent in the β position (β-aryl or β-alkyl). Application of the same reaction conditions to both families of enals may result in erratic levels of asymmetric induction in the reactions of β-aryl enals or low reactivity with β-alkyl enals. A systematic analysis of this behavior using phenylacetic acid derivatives as case studies has led us to find a general trend: the different problems found for β-aryl and β-alkyl enals depend on the acidity of the nucleophile, and the outcome of the reaction for both types of enals can be improved substantially by careful choice of catalyst, solvent, and additive. Furthermore, this study has allowed us to understand subtle aspects of this transformation and has enabled the formulation of a general and reliable protocol to obtain high yields and enantioselectivities consistently, regardless of the acidity of the nucleophile and the nature of the substituent (aromatic or aliphatic) at the β positionWe thank CTQ-2009-12168, CAM (AVANCAT CS2009/PPQ-1634), UAM-CAM (CCG10-UAM/PPQ-5769), CTQ-2012-35957, CTQ2015-63997-C2-1-P, CTQ2016-78779-R and FOTOCARBON-CAM S2013/MIT-2841 for financial support. S.D. thanks the Comunidad Autónoma de Madrid (CAM), and E.R. and S.M. thank MICINN, for predoctoral fellowships. P.M. thanks MICINN for a Ramón y Cajal contract and the EU for a Marie Curie grant (CIG: HYPERCAT-304228American Chemical SocietyDepartamento de Química OrgánicaDepartamento de QuímicaFacultad de Ciencias20172017-11-08research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/681765https://dx.doi.org/10.1021/acscatal.7b02806reponame: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:10486/6817652026-06-23T12:46:27Z |
| dc.title.none.fl_str_mv |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| title |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| spellingShingle |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation Duce, Sara Acidity Asymmetric organocatalysis Enals Iminium activation Michael addition Química |
| title_short |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| title_full |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| title_fullStr |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| title_full_unstemmed |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| title_sort |
The Acidity of a Carbon Nucleophile Dictates Enantioselectivity and Reactivity in Michael Additions to Aromatic and Aliphatic Enals via Iminium Activation |
| dc.creator.none.fl_str_mv |
Duce, Sara Alonso Montero, María Inés Lamsabhi, Al Mokhtar Rodrigo, Eduardo Morales, Sara García Ruano, José Luis Poveda, Ana Mauleón Pérez, Pablo Cid de la Plata, María Belén |
| author |
Duce, Sara |
| author_facet |
Duce, Sara Alonso Montero, María Inés Lamsabhi, Al Mokhtar Rodrigo, Eduardo Morales, Sara García Ruano, José Luis Poveda, Ana Mauleón Pérez, Pablo Cid de la Plata, María Belén |
| author_role |
author |
| author2 |
Alonso Montero, María Inés Lamsabhi, Al Mokhtar Rodrigo, Eduardo Morales, Sara García Ruano, José Luis Poveda, Ana Mauleón Pérez, Pablo Cid de la Plata, María Belén |
| author2_role |
author author author author author author author author |
| dc.contributor.none.fl_str_mv |
Departamento de Química Orgánica Departamento de Química Facultad de Ciencias |
| dc.subject.none.fl_str_mv |
Acidity Asymmetric organocatalysis Enals Iminium activation Michael addition Química |
| topic |
Acidity Asymmetric organocatalysis Enals Iminium activation Michael addition Química |
| description |
The Michael addition of activated methylenes to β-substituted α,β-unsaturated aldehydes (enals) via iminium catalysis takes place following reactivity and enantioselectivity patterns which depend on the electronic nature of the substituent in the β position (β-aryl or β-alkyl). Application of the same reaction conditions to both families of enals may result in erratic levels of asymmetric induction in the reactions of β-aryl enals or low reactivity with β-alkyl enals. A systematic analysis of this behavior using phenylacetic acid derivatives as case studies has led us to find a general trend: the different problems found for β-aryl and β-alkyl enals depend on the acidity of the nucleophile, and the outcome of the reaction for both types of enals can be improved substantially by careful choice of catalyst, solvent, and additive. Furthermore, this study has allowed us to understand subtle aspects of this transformation and has enabled the formulation of a general and reliable protocol to obtain high yields and enantioselectivities consistently, regardless of the acidity of the nucleophile and the nature of the substituent (aromatic or aliphatic) at the β position |
| publishDate |
2017 |
| dc.date.none.fl_str_mv |
2017 2017-11-08 |
| 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/10486/681765 https://dx.doi.org/10.1021/acscatal.7b02806 |
| url |
http://hdl.handle.net/10486/681765 https://dx.doi.org/10.1021/acscatal.7b02806 |
| 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_ |
1869418987256807424 |
| score |
15.300724 |