Author, as appears in the article.: Segovia, Cristina M; Porto, Luana L T N; Casasus, Paula; Bascuas, Isabel; Ahmad, Amena; Mestre, Jordi; Bernus, Miguel; Castillon, Sergio; Baker, R Tom; Boutureira, Omar
Department: Química Analítica i Química Orgànica
URV's Author/s: Bascuas Jiménez De Bagües, Isabel / Bernús Pérez, Miguel / Boutureira Martín, Omar / Casasús Pascua, Paula / Castillón Miranda, Sergio / Mestre Ventura, Jordi
Keywords: Aryl iodides Carbohydrates Copper Cross-coupling Cucf3 Derivative Difluoromethylation Fluorine Glycals Halides Pentafluoroethyl copper Perfluoroalkyl Reagents Tetrafluoroethylatio Tetrafluoroethylation Trifluoromethylation
Abstract: In this study, we have developed a metal-mediated synthetic method for incorporating the 1,1,2,2-tetrafluoroethyl (CF2CF2H) motif into unactivated, electron-rich alkenyl iodides using cross-coupling reactions. We discovered that the stable Cu(CF2CF2H)(PPh2Me)(3) complex, while unreactive with these substrates, serves as a P-ligated reservoir for the formation of solvent-stabilized "ligandless" and reactive CuCF2CF2H species. This transformation occurs upon addition of CuBr, which partially scavenges the P-ligand in the form of CuBr(PPh2Me)(3). The resulting in situ generated solvent stabilized "ligandless" system significantly enhances the reactivity of the complex, particularly towards challenging electron-rich substrates. This advancement enables the synthesis of HCF2CF2-glycals, as well as nucleosides/nucleobases and arenes.
Thematic Areas: Astronomia / física Biodiversidade Catalysis Chemistry, applied Chemistry, organic Ciência de alimentos Ciências biológicas ii Engenharias ii Engenharias iv Materiais Organic chemistry Química
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: sergio.castillon@urv.cat miguel.bernus@urv.cat miguel.bernus@urv.cat omar.boutureira@urv.cat isabel.bascuas@estudiants.urv.cat isabel.bascuas@estudiants.urv.cat miguel.bernus@urv.cat paula.casasus@urv.cat
Author identifier: 0000-0002-0690-7549 0000-0003-0302-0720 0000-0003-0302-0720 0000-0002-0768-8309 0000-0003-0302-0720
Record's date: 2024-11-30
Papper version: info:eu-repo/semantics/publishedVersion
Papper original source: Advanced Synthesis & Catalysis. 366 (12): 2684-2690
APA: Segovia, Cristina M; Porto, Luana L T N; Casasus, Paula; Bascuas, Isabel; Ahmad, Amena; Mestre, Jordi; Bernus, Miguel; Castillon, Sergio; Baker, R Tom (2024). Tetrafluoroethylation of Electron-Rich Alkenyl Iodides Enabled by in situ Generation of Solvent-Stabilized "Ligandless" CuCF2CF2H. Advanced Synthesis & Catalysis, 366(12), 2684-2690. DOI: 10.1002/adsc.202301409
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Entity: Universitat Rovira i Virgili
Journal publication year: 2024
Publication Type: Journal Publications
Repositori URV