Cyclic Regulation of the Sulfilimine Bond in Peptides and NC1 Hexamers via the HOBr/HSe Conjugated System.

Anal Chem

College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals , Shandong Normal University, Jinan 250014 , People's Republic of China.

Published: August 2018

The sulfilimine bond (-S═N-), found in the collagen IV scaffold, significantly stabilizes the architecture via the formation of sulfilimine cross-links. However, precisely governing the formation and breakup process of the sulfilimine bond in living organisms for better life functions still remains a challenge. Hence, we established a new way to regulate the breaking and formation of the sulfilimine bond through hydrogen selenide (HSe) and hypobromous acid (HOBr), which can be easily controlled at simulated physiological conditions. This novel strategy provides a circulation regulation system to modulate the sulfilimine bond in peptides and NC1 hexamers, which can offer a substantial system for further study of the physiological function of collagen IV.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.analchem.8b02228DOI Listing

Publication Analysis

Top Keywords

sulfilimine bond
20
bond peptides
8
peptides nc1
8
nc1 hexamers
8
formation sulfilimine
8
sulfilimine
6
bond
5
cyclic regulation
4
regulation sulfilimine
4
hexamers hobr/hse
4

Similar Publications

Intermolecular sulfur atom transfer cascade enabled late-stage introduction of sulfilimines into peptides.

Chem Sci

September 2024

Key Laboratory of Preclinical Study for New Drugs of Gansu Province, School of Basic Medical Sciences & Research Unit of Peptide Science, Chinese Academy of Medical Sciences, 2019RU066, Lanzhou University Lanzhou 730000 China

Sulfilimines, a privileged class of -S(iv)[double bond, length as m-dash]N- functional groups found in nature, have been exploited as valuable building blocks in organic synthesis and as pharmacophores in drug discovery, and have aroused significant interest in the chemical community. Nevertheless, strategies for late-stage introduction of sulfilimines into peptides and proteins have still met with limited success. Herein, we have developed a method of introducing biological sulfilimine fragments into peptides by an intermolecular sulfur atom transfer cascade reaction, utilizing hydroxylamine condensed with the acid moieties of peptides and varied diaryl disulfides.

View Article and Find Full Text PDF

Radical-mediated click-clip reactions.

Science

September 2024

Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China.

Click reactions, which are characterized by rapid, high-yielding, and highly selective coupling of two reaction partners, are powerful tools in synthesis but are rarely reversible. Innovative strategies that reverse such couplings in a precise and on-demand manner, enabling a click-clip sequence, would greatly expand the technique's versatility. Herein, a click and clip reaction pair is demonstrated by manipulation of a sulfilimine linkage.

View Article and Find Full Text PDF

Ligand-Enabled Copper-Catalyzed Ullmann-Type S-C Bond Formation to Access Sulfilimines.

Org Lett

September 2024

School of Pharmaceutical and Chemical Engineering & Institute for Advanced Studies, Taizhou University, Taizhou 318000, Zhejiang, China.

A copper-catalyzed Ullmann-type cross-coupling reaction of sulfenamides with aryl iodides is developed. The key to success is the use of a 2-methylnaphthalen-1-amine-derived amide ligand, which enables the formation of an S-C bond to access functionalized sulfilimines in good to excellent yields at room temperature. This method has the advantages of mild conditions, a broad substrate scope, good functional group compatibility, and high chemoselectivity.

View Article and Find Full Text PDF

The one-pot synthesis of λ-dibenzothiophen-5-imino-N-dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh(esp) (esp=α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid) generating a Rh-coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good yields.

View Article and Find Full Text PDF

Decarboxylative Radical Sulfilimination via Photoredox, Copper, and Brønsted Base Catalysis.

Angew Chem Int Ed Engl

February 2024

State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.

Sulfilimines, the aza-variants of sulfoxides, are key structural motifs in natural products, pharmaceuticals, and agrochemicals; and sulfilimine synthesis is therefore important in organic chemistry. However, methods for radical sulfilimination remain elusive, and as a result, the structural diversity of currently available sulfilimines is limited. Herein, we report the first protocol for decarboxylative radical sulfilimination reactions between sulfenamides and N-hydroxyphthalimide esters of primary, secondary, and tertiary alkyl carboxylic acids, which were achieved via a combination of photoredox, copper, and Brønsted base catalysis.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!