o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations

Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) react with halogenating reagents (PhICl2, Br2, I2) (2) to give the corresponding o-halogenated amino acids C6H3(X)R1C(R2)(R3)N(R4)2 (3). The reaction is general and tolerates a variety of functional gro...

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Authors: Laga, Eduardo, Nieto, Sonia, Cativiela, Carlos, Urriolabeitia, Esteban P.
Format: article
Status:Published version
Publication Date:2025
Country:España
Institution:Universidad de Zaragoza
Repository:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:150732
Online Access:http://zaguan.unizar.es/record/150732
Access Level:Open access
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spelling o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and LimitationsLaga, EduardoNieto, SoniaCativiela, CarlosUrriolabeitia, Esteban P.Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) react with halogenating reagents (PhICl2, Br2, I2) (2) to give the corresponding o-halogenated amino acids C6H3(X)R1C(R2)(R3)N(R4)2 (3). The reaction is general and tolerates a variety of functional groups (R1 to R4) at the aryl ring, the Cα, and the N atom. On the other hand, the reaction of [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) with PhI(OAc)2 in the presence of a variety of alcohols R5OH (4) gives the o-alkoxylated phenylglycines C6H3(OR5)R1C(R2)(R3)N(R4)2 (5), also as a general process. A partial loss of the enantiomeric excess is observed when the starting phenylglycine is enantiomerically pure, this arising from the formation of bridging azavinylidene (6) and imine intermediate species (7), which were characterized by X-ray diffraction methods.2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/150732reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E17-23Rinfo:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1507322026-05-29T13:59:51Z
dc.title.none.fl_str_mv o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
title o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
spellingShingle o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
Laga, Eduardo
title_short o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
title_full o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
title_fullStr o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
title_full_unstemmed o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
title_sort o-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
dc.creator.none.fl_str_mv Laga, Eduardo
Nieto, Sonia
Cativiela, Carlos
Urriolabeitia, Esteban P.
author Laga, Eduardo
author_facet Laga, Eduardo
Nieto, Sonia
Cativiela, Carlos
Urriolabeitia, Esteban P.
author_role author
author2 Nieto, Sonia
Cativiela, Carlos
Urriolabeitia, Esteban P.
author2_role author
author
author
description Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) react with halogenating reagents (PhICl2, Br2, I2) (2) to give the corresponding o-halogenated amino acids C6H3(X)R1C(R2)(R3)N(R4)2 (3). The reaction is general and tolerates a variety of functional groups (R1 to R4) at the aryl ring, the Cα, and the N atom. On the other hand, the reaction of [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) with PhI(OAc)2 in the presence of a variety of alcohols R5OH (4) gives the o-alkoxylated phenylglycines C6H3(OR5)R1C(R2)(R3)N(R4)2 (5), also as a general process. A partial loss of the enantiomeric excess is observed when the starting phenylglycine is enantiomerically pure, this arising from the formation of bridging azavinylidene (6) and imine intermediate species (7), which were characterized by X-ray diffraction methods.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/150732
url http://zaguan.unizar.es/record/150732
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA/E17-23R
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
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