Enabling C7 Methylation and Arylation of the Indolyl Core via P(III)‐Directed C−H Functionalization DOI
Christopher B. Kelly, Rosaura Padilla‐Salinas, Wenyong Chen

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(9), С. 2044 - 2055

Опубликована: Фев. 26, 2024

Abstract Peripheral editing of complex molecules via C−H functionalization removes the pervasive retrosynthetic bias toward pre‐functionalization and taps into innate, often subtle, stereoelectronic differences between linkages. Using this approach, bioactive residues can be modified without being beholden to lengthy sequences, thus allowing biochemical hypotheses interrogated on accelerated timelines. Herein, paradigm is leveraged tackle C7 biologically important tryptophan core. The devised process, which was expanded indolyl (and related) systems, utilizes an N ‐bound unsymmetrical “designer” phosphine direct desired position while maintaining operational ease directing group installation/removal. Quantum mechanically calculated steric properties activation free energies suggest that hindered enough for favoring over deactivation pathways but still easily cleaved by nucleophiles. In addition, process enables methylation, cyclopropanation, arylation yield unnatural amino acid (UAA) building blocks. As a testament versatility method, solid phase peptide synthesis (SPPS)‐ready phosphinated incorporated pentapeptide functionalization/dephosphination sequence executed with ease. utility “on‐peptide” exhibited through late‐stage several pentapeptides diverse set substituents on‐ off‐resin.

Язык: Английский

Post-synthetic Chemical Functionalization of Peptides DOI

Stephanie A. Barros,

Rosaura Padilla‐Salinas, Irini Abdiaj

и другие.

Elsevier eBooks, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Enabling C7 Methylation and Arylation of the Indolyl Core via P(III)‐Directed C−H Functionalization DOI
Christopher B. Kelly, Rosaura Padilla‐Salinas, Wenyong Chen

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(9), С. 2044 - 2055

Опубликована: Фев. 26, 2024

Abstract Peripheral editing of complex molecules via C−H functionalization removes the pervasive retrosynthetic bias toward pre‐functionalization and taps into innate, often subtle, stereoelectronic differences between linkages. Using this approach, bioactive residues can be modified without being beholden to lengthy sequences, thus allowing biochemical hypotheses interrogated on accelerated timelines. Herein, paradigm is leveraged tackle C7 biologically important tryptophan core. The devised process, which was expanded indolyl (and related) systems, utilizes an N ‐bound unsymmetrical “designer” phosphine direct desired position while maintaining operational ease directing group installation/removal. Quantum mechanically calculated steric properties activation free energies suggest that hindered enough for favoring over deactivation pathways but still easily cleaved by nucleophiles. In addition, process enables methylation, cyclopropanation, arylation yield unnatural amino acid (UAA) building blocks. As a testament versatility method, solid phase peptide synthesis (SPPS)‐ready phosphinated incorporated pentapeptide functionalization/dephosphination sequence executed with ease. utility “on‐peptide” exhibited through late‐stage several pentapeptides diverse set substituents on‐ off‐resin.

Язык: Английский

Процитировано

1