Dimethyl Sulfoxide/Visible-Light Comediated Chemoselective C-S Bond Formation Between Tryptophans and Thiophenols Enables Site-Selective Functionalization of Peptides  

作　　者：Guangjun Bao Peng Wang Jingyue Li Xinyi Song Tingli Yu Jiao Zhang Yiping Li Zeyuan He Ruiyao E Xiaokang Miao Junqiu Xie Jingman Ni Rui Wang Wangsheng Sun 

机构地区：[1]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 [2]State Key Laboratory of Bioactive Substance and Function of Natural Medicines,Institute of Materia Medica,Chinese Academy of Medical Sciences and Peking Union Medical College,Beijing 100050

出　　处：《CCS Chemistry》2024年第6期1547-1556,共10页中国化学会会刊（英文）

基　　金：the CAMS Innovation Fund for Medical Sciences(CIFMS)(grant nos.2019-I2M-5-074,2021-I2M-1-026,2021-I2M-3-001,and 2022-I2M-2-002);the National Natural Science Foundation of China(grant nos.81773564,82173678 and 22307052);the Program for Chang-Jiang Scholars and Innovative Research Team in University(grant no.IRT_15R27);the fellowship of China Postdoctoral Science Foundation(grant no.2021M701533);the Gansu Science and Technology Program(grant nos.23JRRA1103,22JR5RA502,and 21JR7RA449).

摘　　要：Late-stage peptide modification showcases a huge potential for the construction of peptide libraries,and the investigation of structure-activity relationships.Herein we report a dimethyl sulfoxide/visible light comediated chemoselective modification of tryptophan residue by forging the C-S structure using thiophenols irradiated with blue light-emitting diodes at room temperature.This method shows excellent chemoselectivity toward the C-2 position of the tryptophan residue and good compatibility with diverse thiophenol derivatives bearing various functional groups.Both protected oligopeptides and unmasked bioactive peptides smoothly underwent site-selective modification,furnishing the corresponding products.Above all,this study provides a new competent toolkit for late-stage peptide modification,labelling,and peptide-drug conjugation and provides a clue for protein bioconjugation.

关 键 词：peptide modification late-stage diversification photocatalysis TRYPTOPHAN THIOPHENOL 

分 类 号：O62[理学—有机化学]