BODIPY Peptide Labeling by Late‐Stage C(sp3)−H Activation DOI
Wei Wang, Mélanie M. Lorion, Oscar Martinazzoli

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(33), P. 10554 - 10558

Published: June 8, 2018

Abstract Late‐stage BODIPY diversification of structurally complex amino acids and peptides was accomplished by racemization‐free palladium‐catalyzed C(sp 3 )−H activation. Transformative fluorescence modification proved viable triazole‐assisted arylation in a chemo‐ site‐selective fashion, providing modular access to novel peptide sensors.

Language: Английский

Manganese(I)‐Catalyzed Regioselective C−H Allenylation: Direct Access to 2‐Allenylindoles DOI
Qingquan Lu,

Steffen Greßies,

Felix J. R. Klauck

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(23), P. 6660 - 6664

Published: May 2, 2017

Abstract A Mn I ‐catalyzed regioselective C−H allenylation is reported that allows a broad range of 2‐allenylindoles to be synthesized regioselectively on gram scale under simple conditions. Notably, highly efficient chirality transfer was observed (up 93 % ee ) in this transformation. This procedure further found allow, for the first time, direct preparation ketones by activation. Mechanistic investigations revealed precoordination oxygen atom manganese center as well congested tertiary carbon propargylic carbonates play crucial role.

Language: Английский

Citations

171
Visible‐Light‐Promoted C(sp3)−H Alkylation by Intermolecular Charge Transfer: Preparation of Unnatural α‐Amino Acids and Late‐Stage Modification of Peptides DOI
Chao Wang,

Rupeng Qi,

Hongxiang Xue

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(19), P. 7461 - 7466

Published: Feb. 20, 2020

Disclosed herein is the visible-light-promoted deaminative C(sp3 )-H alkylation of glycine and peptides using Katritzky salts as electrophiles. Simple reaction conditions excellent functional-group tolerance provide a general strategy for efficient preparation unnatural α-amino acids precise modification with α-amino-acid residues. Mechanistic studies suggest that intermolecular charge transfer within glycine-Katritzky salt electron donor-acceptor (EDA) complex induces single-electron process without assistance photocatalyst.

Language: Английский

Citations

157
Histidine-Specific Peptide Modification via Visible-Light-Promoted C–H Alkylation DOI
Xiaoping Chen,

Farong Ye,

Xiaosheng Luo

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(45), P. 18230 - 18237

Published: Oct. 21, 2019

Histidine (His) carries a unique heteroaromatic imidazole side chain and plays irreplaceable functional roles in peptides proteins. Existing strategies for site-selective histidine modification predominantly rely on the N-substitution reactions of moderately nucleophilic group, which inherently suffers from interferences lysine cysteine residues. Chemoselective remains one most difficult challenges peptide chemistry. Herein, we report via radical-mediated chemoselective C–H alkylation using C4-alkyl-1,4-dihydropyridine (DHP) reagents under visible-light-promoted conditions. The method exploits electrophilic reactivity ring Minisci-type reaction pathway. This exhibits an exceptionally broad scope both DHP reagents. Its utility has been demonstrated series important drugs, complex natural products, small protein. Distinct reactions, unsubstituted nitrogen groups modified are conserved alkylated products.

Language: Английский

Citations

155
Recent advances in chemical protein synthesis: method developments and biological applications DOI
Suwei Dong, Ji‐Shen Zheng, Yiming Li

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(4), P. 1060 - 1096

Published: March 12, 2024

Language: Английский

Citations

60
Tryptophan-specific modification and diversification of peptides and proteins DOI
S K Kundu, A. Bandyopadhyay, Rajib Sarkar

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an account of the tryptophan-specific conjugation peptides and proteins its extensive application in imaging living cells, radiolabelling proteins, protein engineering, etc .

Language: Английский

Citations

2
Palladium(II)‐Catalyzed Site‐Selective C(sp3)−H Alkynylation of Oligopeptides: A Linchpin Approach for Oligopeptide–Drug Conjugation DOI
Tao Liu, Jennifer X. Qiao, Michael A. Poss

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(36), P. 10924 - 10927

Published: July 17, 2017

The palladium(II)-catalyzed C(sp3 )-H alkynylation of oligopeptides was developed with tetrabutylammonium acetate as a key additive. Through molecular design, the acetylene motif served linchpin to introduce broad range carbonyl-containing pharmacophores onto oligopeptides, thus providing chemical tool for synthesis and modification novel oligopeptide-pharmacophore conjugates by C-H functionalization. Dipeptide coprostanol estradiol were synthesized this method potential application in targeted drug delivery tumor cells overexpressed nuclear hormone receptors.

Language: Английский

Citations

163
Broad-Scope Rh-Catalyzed Inverse-Sonogashira Reaction Directed by Weakly Coordinating Groups DOI Creative Commons

Eric Tan,

Ophélie Quinonero, M. Elena de Orbe

et al.

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(3), P. 2166 - 2172

Published: Jan. 30, 2018

We report the alkynylation of C(sp2)-H bonds with bromoalkynes (inverse-Sonogashira reaction) directed by synthetically useful ester, ketone, and ether groups under rhodium catalysis. Other less common directing such as amine, thioether, sulfoxide, sulfone, phenol carbamate are also suitable groups. Mechanistic studies indicate that reaction proceeds a turnover-limiting C-H activation step via an electrophilic-type substitution.

Language: Английский

Citations

161
Methylenecyclopropane Annulation by Manganese(I)‐Catalyzed Stereoselective C−H/C−C Activation DOI
Yu‐Feng Liang, Valentin Müller, Weiping Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(32), P. 9415 - 9419

Published: June 12, 2017

Abstract C−H/C−C functionalizations with methylenecyclopropanes (MCPs) were accomplished a versatile base‐metal catalyst. A robust manganese(I) complex enabled the expedient annulation of MCPs by synthetically meaningful ketimines to deliver, upon one‐pot hydroarylation, densely substituted polycylic anilines in step‐economical fashion. Mechanistic studies provided strong support for facile organometallic C−H manganation, while typical cobalt, ruthenium, rhodium, and palladium catalysts found completely ineffective.

Language: Английский

Citations

143
Manganese(I)‐Catalyzed Regio‐ and Stereoselective 1,2‐Diheteroarylation of Allenes: Combination of C−H Activation and Smiles Rearrangement DOI
Shiyong Chen, Xiang‐Lei Han, Jia‐Qiang Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(33), P. 9939 - 9943

Published: June 20, 2017

Abstract Heteroarenes are important structural motif in functional molecules. A Mn I ‐catalyzed 1,2‐diheteroarylation of allenes via a C−H activation/Smiles rearrangement cascade is presented. The reaction occurred under additive‐free or even solvent‐free conditions, which allowed the creation two C−C and one C−N bonds single operation. series structurally diverse bicyclic tricyclic compounds bearing an exocyclic double bond were constructed good to excellent efficiency. decarboxylative ring‐opening products led facile synthesis vicinal biheteroaryls. Synthetic applications demonstrated preliminary mechanistic studies conducted.

Language: Английский

Citations

143
Air‐Stable Manganese(I)‐Catalyzed C−H Activation for Decarboxylative C−H/C−O Cleavages in Water DOI
Hui Wang, Mélanie M. Lorion, Lutz Ackermann

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(22), P. 6339 - 6342

Published: May 5, 2017

The decarboxylative C-H/C-O functionalization was accomplished by air- and water-tolerant manganese(I) catalysis. versatile C-H allylation occurred facile organometallic metalation on indoles, arenes, amino acids synthetically meaningful aryl ketimines with ample substrate scope high levels of chemo-, site- regio-selectivity.

Language: Английский

Citations

141