Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids
Despite the emergence of catalytic C(sp3 )−H arylation at the remote δ-position via challenging six-membered ring cyclometalation, the requirement of blocking the more reactive γ-position represents a restricting limitation. The use of the removable N-(2-pyridyl)sulfonyl directing group provides a v...
| Autores: | , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/695363 |
| Acceso en línea: | http://hdl.handle.net/10486/695363 https://dx.doi.org/10.1021/acscatal.1c00250 |
| Access Level: | acceso abierto |
| Palabra clave: | Remote C(sp3 )−H arylation Palladium-catalysis α-amino acid 2-pyridylsulfonyl directing group Late-stage functionalization Peptide Química |
| id |
ES_10a727df548a71255cfa1a84c856daae |
|---|---|
| oai_identifier_str |
oai:repositorio.uam.es:10486/695363 |
| network_acronym_str |
ES |
| network_name_str |
España |
| repository_id_str |
|
| spelling |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino AcidsMartínez-Mingo, MarioGarcía-Viada, AndrésAlonso Montero, María InésRodríguez Garrido, NuriaGómez Arrayas, Ramón JesúsCarretero Gonzálvez, Juan CarlosRemote C(sp3 )−H arylationPalladium-catalysisα-amino acid2-pyridylsulfonyl directing groupLate-stage functionalizationPeptideQuímicaDespite the emergence of catalytic C(sp3 )−H arylation at the remote δ-position via challenging six-membered ring cyclometalation, the requirement of blocking the more reactive γ-position represents a restricting limitation. The use of the removable N-(2-pyridyl)sulfonyl directing group provides a viable solution to this challenge, expanding the scope of the Pd-catalyzed δ-C−H arylation of α-amino acid and amine derivatives with (hetero)aryl iodides. This method is compatible with complex, multifunctional structures at either reaction partner. Experimental and density functional theory studies provide insights about the underlying factors controlling site selectivityWe thank the Ministerio de Economía, Industria y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (FEDER, UE) (Project CTQ2015-66954-P) and Ministerio de Ciencia e Innovación (MICINN)/FEDER, UE (Agencia Estatal de Investigación/Project PGC2018- 098660-B-I00) for the financial supportAmerican Chemical SocietyDepartamento de Química OrgánicaFacultad de Ciencias20212021-04-19research articlehttp://purl.org/coar/resource_type/c_2df8fbb1AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/695363https://dx.doi.org/10.1021/acscatal.1c00250reponame: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:10486/6953632026-06-23T12:46:27Z |
| dc.title.none.fl_str_mv |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| title |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| spellingShingle |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids Martínez-Mingo, Mario Remote C(sp3 )−H arylation Palladium-catalysis α-amino acid 2-pyridylsulfonyl directing group Late-stage functionalization Peptide Química |
| title_short |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| title_full |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| title_fullStr |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| title_full_unstemmed |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| title_sort |
Overcoming the Necessity of γ-Substitution in δ-C(sp3)–H Arylation: Pd-Catalyzed Derivatization of α-Amino Acids |
| dc.creator.none.fl_str_mv |
Martínez-Mingo, Mario García-Viada, Andrés Alonso Montero, María Inés Rodríguez Garrido, Nuria Gómez Arrayas, Ramón Jesús Carretero Gonzálvez, Juan Carlos |
| author |
Martínez-Mingo, Mario |
| author_facet |
Martínez-Mingo, Mario García-Viada, Andrés Alonso Montero, María Inés Rodríguez Garrido, Nuria Gómez Arrayas, Ramón Jesús Carretero Gonzálvez, Juan Carlos |
| author_role |
author |
| author2 |
García-Viada, Andrés Alonso Montero, María Inés Rodríguez Garrido, Nuria Gómez Arrayas, Ramón Jesús Carretero Gonzálvez, Juan Carlos |
| author2_role |
author author author author author |
| dc.contributor.none.fl_str_mv |
Departamento de Química Orgánica Facultad de Ciencias |
| dc.subject.none.fl_str_mv |
Remote C(sp3 )−H arylation Palladium-catalysis α-amino acid 2-pyridylsulfonyl directing group Late-stage functionalization Peptide Química |
| topic |
Remote C(sp3 )−H arylation Palladium-catalysis α-amino acid 2-pyridylsulfonyl directing group Late-stage functionalization Peptide Química |
| description |
Despite the emergence of catalytic C(sp3 )−H arylation at the remote δ-position via challenging six-membered ring cyclometalation, the requirement of blocking the more reactive γ-position represents a restricting limitation. The use of the removable N-(2-pyridyl)sulfonyl directing group provides a viable solution to this challenge, expanding the scope of the Pd-catalyzed δ-C−H arylation of α-amino acid and amine derivatives with (hetero)aryl iodides. This method is compatible with complex, multifunctional structures at either reaction partner. Experimental and density functional theory studies provide insights about the underlying factors controlling site selectivity |
| publishDate |
2021 |
| dc.date.none.fl_str_mv |
2021 2021-04-19 |
| 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/10486/695363 https://dx.doi.org/10.1021/acscatal.1c00250 |
| url |
http://hdl.handle.net/10486/695363 https://dx.doi.org/10.1021/acscatal.1c00250 |
| 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_ |
1869403521872297984 |
| score |
15.300719 |