<i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations
Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C<sub>6</sub>H<sub>3</sub>R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>)...
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2025-01-01
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| author | Eduardo Laga Sonia Nieto Carlos Cativiela Esteban P. Urriolabeitia |
| author_facet | Eduardo Laga Sonia Nieto Carlos Cativiela Esteban P. Urriolabeitia |
| author_sort | Eduardo Laga |
| collection | DOAJ |
| description | Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C<sub>6</sub>H<sub>3</sub>R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) react with halogenating reagents (PhICl<sub>2</sub>, Br<sub>2</sub>, I<sub>2</sub>) (<b>2</b>) to give the corresponding o-halogenated amino acids C<sub>6</sub>H<sub>3</sub>(X)R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub> (<b>3</b>). The reaction is general and tolerates a variety of functional groups (R<sub>1</sub> to R<sub>4</sub>) at the aryl ring, the Cα, and the N atom. On the other hand, the reaction of [Pd(μ-Cl)(C<sub>6</sub>H<sub>3</sub>R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) with PhI(OAc)<sub>2</sub> in the presence of a variety of alcohols R<sub>5</sub>OH (<b>4</b>) gives the o-alkoxylated phenylglycines C<sub>6</sub>H<sub>3</sub>(OR<sub>5</sub>)R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub> (<b>5</b>), 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 (<b>6</b>) and imine intermediate species (<b>7</b>), which were characterized by X-ray diffraction methods. |
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| institution | Kabale University |
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| publishDate | 2025-01-01 |
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| spelling | doaj-art-e3d85b6c58a04023ac8548b3545506ba2025-01-24T13:43:12ZengMDPI AGMolecules1420-30492025-01-0130223610.3390/molecules30020236<i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and LimitationsEduardo Laga0Sonia Nieto1Carlos Cativiela2Esteban P. Urriolabeitia3Instituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC—Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC—Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC—Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, SpainInstituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC—Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, SpainOrthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C<sub>6</sub>H<sub>3</sub>R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) react with halogenating reagents (PhICl<sub>2</sub>, Br<sub>2</sub>, I<sub>2</sub>) (<b>2</b>) to give the corresponding o-halogenated amino acids C<sub>6</sub>H<sub>3</sub>(X)R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub> (<b>3</b>). The reaction is general and tolerates a variety of functional groups (R<sub>1</sub> to R<sub>4</sub>) at the aryl ring, the Cα, and the N atom. On the other hand, the reaction of [Pd(μ-Cl)(C<sub>6</sub>H<sub>3</sub>R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub>]<sub>2</sub> (<b>1</b>) with PhI(OAc)<sub>2</sub> in the presence of a variety of alcohols R<sub>5</sub>OH (<b>4</b>) gives the o-alkoxylated phenylglycines C<sub>6</sub>H<sub>3</sub>(OR<sub>5</sub>)R<sub>1</sub>C(R<sub>2</sub>)(R<sub>3</sub>)N(R<sub>4</sub>)<sub>2</sub> (<b>5</b>), 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 (<b>6</b>) and imine intermediate species (<b>7</b>), which were characterized by X-ray diffraction methods.https://www.mdpi.com/1420-3049/30/2/236amino acidspalladiumC-H bond activationhalogenationalkoxylation |
| spellingShingle | Eduardo Laga Sonia Nieto Carlos Cativiela Esteban P. Urriolabeitia <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations Molecules amino acids palladium C-H bond activation halogenation alkoxylation |
| title | <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations |
| title_full | <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations |
| title_fullStr | <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations |
| title_full_unstemmed | <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations |
| title_short | <i>o</i>-Halogenation and -Alkoxylation of Phenylglycine Derivatives by Pd-Mediated C-H Functionalization: Scope and Limitations |
| title_sort | i o i halogenation and alkoxylation of phenylglycine derivatives by pd mediated c h functionalization scope and limitations |
| topic | amino acids palladium C-H bond activation halogenation alkoxylation |
| url | https://www.mdpi.com/1420-3049/30/2/236 |
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