{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Li BY"],"funding":["Bundesministerium für Bildung und Forschung","China Scholarship Council","Herculesstichting","Ministerium für Kultur und Wissenschaft des Landes Nordrhein-Westfalen","KU Leuven","Fonds Wetenschappelijk Onderzoek","Vrije Universiteit Brussel"],"pagination":["2270-2279"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8864708"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["13(8)"],"pubmed_abstract":["Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the <i>ex situ</i> generation of trifluoromethanesulfonyl fluoride (CF<sub>3</sub>SO<sub>2</sub>F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the S<sup>VI</sup>-F connector with a S[double bond, length as m-dash]O → S[double bond, length as m-dash]NR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H<sub>2</sub>O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols <i>vs.</i> amine groups, a phenomenon best explained-using <i>ab initio</i> metadynamics simulations-by a hydrogen bonded termolecular transition state for the CF<sub>3</sub>SO<sub>2</sub>F triflylation of amines."],"journal":["Chemical science"],"pubmed_title":["SuFEx-enabled, chemoselective synthesis of triflates, triflamides and triflimidates."],"pmcid":["PMC8864708"],"funding_grant_id":["G0D6221N","20100225–7","1SA1121N","DOA/2020/013","12ZL820N","1185221N","12F4416N"],"pubmed_authors":["Voets L","Li BY","Verhelst SHL","Van Lommel R","Alonso M","De Borggraeve WM","Hoppenbrouwers F","Demaerel J"],"additional_accession":[]},"is_claimable":false,"name":"SuFEx-enabled, chemoselective synthesis of triflates, triflamides and triflimidates.","description":"Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the <i>ex situ</i> generation of trifluoromethanesulfonyl fluoride (CF<sub>3</sub>SO<sub>2</sub>F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the S<sup>VI</sup>-F connector with a S[double bond, length as m-dash]O → S[double bond, length as m-dash]NR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H<sub>2</sub>O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols <i>vs.</i> amine groups, a phenomenon best explained-using <i>ab initio</i> metadynamics simulations-by a hydrogen bonded termolecular transition state for the CF<sub>3</sub>SO<sub>2</sub>F triflylation of amines.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Feb","modification":"2025-04-19T13:20:16.485Z","creation":"2025-04-19T13:20:16.485Z"},"accession":"S-EPMC8864708","cross_references":{"pubmed":["35310484"],"doi":["10.1039/d1sc06267k"]}}