Triflic Acid-Mediated Chemoselective Indole C2-Heteroarylation of Peptide Tryptophan Residues by Triazine DOI
Jian Li, Qi-Long Hu,

Jia-Shu Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Peptide modification provides opportunities to afford peptides with designed functions. Among the proteogenic amino acids, tryptophan represents an ideal and attractive target for peptide because of exclusive chemical reactivity its unique indole structure. Herein, we reported C2 position-selective transition-metal-free approach derivatives tryptophan-containing by triazine via triflic acid activation that incorporated functional group could act as orthogonal handle further bioconjugation inverse electron demand Diels–Alder reaction.

Language: Английский

Dehydrogenative Coupling of Alcohols with Internal Alkynes under Nickel Catalysis: An Access to β-Deuterated Branched Ketones DOI
Murugan Subaramanian,

Chandrakant Gouda,

Triptesh Kumar Roy

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8294 - 8309

Published: May 13, 2024

In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C–C C–N bond-forming reactions via dehydrogenative borrowing hydrogen strategy traditional transition metal catalysis; however, an acylating agent is rarely reported. Here, we report coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol used agent. This reaction system affords a wide range α-branched aryl ketone derivatives zero waste generation through umpolung strategy. Moreover, have demonstrated chemodivergent applications α-disubstituted ketones to other valuable building blocks, including large-scale β-deuterated branched ketones. Several spectroscopic studies, intermediate identification, density functional theory calculations were performed elucidate mechanism.

Language: Английский

Citations

2
Sulfoxide-mediated Cys-Trp-selective bioconjugation that enables protein labeling and peptide heterodimerization DOI Creative Commons

Daishiro Kobayashi,

Masaya Deda,

Junya Hayashi

et al.

Published: Jan. 8, 2024

A method was developed that enables the magnesium chloride (MgCl2)-activated S-acetamidomethyl cysteine sulfoxide (Cys(Acm)(O)) to induce sp2(C−H) sulfenylation of indole ring Trp residues. The reaction operates under mild acidic conditions using acetic acid or an ionic liquid in a highly Trp-selective manner give Trp-sulfenylated products. Other than Trp, all other proteinogenic amino acids are unreactive conditions. We demonstrated successful application this variety peptides, including lysozyme protein. Furthermore, we achieved Trp-modification monoclonal antibody (trastuzumab®) by MgCl2-mediated liquid. resulting modified exhibited performance comparable parent presence amide moiety Acm group contributes difference chemical behavior between S-Acm and S-p-methoxybenzyl (MBzl)-protected sulfoxide. This is because converted S-chlorocysteine responsible for Trp-sulfenylation less those required S-MBzl Based on rationale, prepared linker possessing oxide moieties subjected hetero dimerization DNA-binding Myc Max peptides containing handle. one-pot/stepwise Cys-Trp conjugation allowed generation heterodimeric Myc/Max DNA binder.

Language: Английский

Citations

1
Sulfoxide‐Mediated Cys‐Trp‐Selective Bioconjugation that Enables Protein Labeling and Peptide Heterodimerization DOI Creative Commons

Daishiro Kobayashi,

Masaya Denda,

Junya Hayashi

et al.

ChemistryEurope, Journal Year: 2024, Volume and Issue: 2(3-4)

Published: May 1, 2024

Abstract A method was developed that enables the magnesium chloride (MgCl 2 )‐activated S ‐acetamidomethyl cysteine sulfoxide (Cys(Acm)(O)) to induce sp (C−H) sulfenylation of indole Trp residues. The reaction operates under mild acidic conditions using acetic acid or an ionic liquid give Trp‐sulfenylated products. Other than Trp, all other proteinogenic amino acids are unreactive conditions. We demonstrated successful application this various peptides, including lysozyme. Furthermore, we achieved Trp‐modification a monoclonal antibody by MgCl ‐mediated in liquid. resulting exhibited performance comparable parent protein. amide moiety Acm group contributes difference chemical behaviors between ‐Acm and S‐p ‐methoxybenzyl (MBzl)‐protected sulfoxides. This is because converted ‐chlorocysteine responsible for Trp‐sulfenylation less those required ‐MBzl sulfoxide. Based on rationale, prepared linker possessing oxide moieties subjected heterodimerization DNA‐binding MYC MAX peptides containing handle. one‐pot/stepwise Cys‐Trp conjugation allowed generation heterodimeric MYC/MAX DNA binder.

Language: Английский

Citations

1
Transition Metal Promoted Brook Rearrangement and its Related Reactions DOI

Fazhou Yang,

Jinbao Wang, Yujie Dong

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 168, P. 134351 - 134351

Published: Nov. 1, 2024

Language: Английский

Citations

1
Triflic Acid-Mediated Chemoselective Indole C2-Heteroarylation of Peptide Tryptophan Residues by Triazine DOI
Jian Li, Qi-Long Hu,

Jia-Shu Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Peptide modification provides opportunities to afford peptides with designed functions. Among the proteogenic amino acids, tryptophan represents an ideal and attractive target for peptide because of exclusive chemical reactivity its unique indole structure. Herein, we reported C2 position-selective transition-metal-free approach derivatives tryptophan-containing by triazine via triflic acid activation that incorporated functional group could act as orthogonal handle further bioconjugation inverse electron demand Diels–Alder reaction.

Language: Английский

Citations

1