The stereoselective synthesis of chlorotrifluoromethylated pyrrolidines was achieved using anodically coupled electrolysis, an electrochemical process that combines two parallel oxidative events in a convergent and productive manner. The bench-stable and commercially available solids CF SO Na and MgCl were used as the functional group sources to generate CF and Cl , respectively, via electrochemical oxidation, and the subsequent reaction of these radicals with the 1,6-enyne substrate was controlled with an earth-abundant Mn catalyst. In particular, the introduction of a chelating ligand allowed for the ene-yne cyclization to take place with high stereochemical control over the geometry of the alkene group in the pyrrolidine product.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/chem.201802167 | DOI Listing |
J Org Chem
January 2021
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, College of Chemistry, Northeast Normal University, Changchun 130024, China.
We report here an alternatively catalytic aminotrifluoromethylation of alkenes using PhICFCl as a bifunctional reagent along with ZnI as a dual catalyst. A combined catalytic strategy was established for the intramolecular aminotrifluoromethylation of 4-pentenamines. As a result, a set of 2-trifluoroethyl-pyrrolidines was obtained in a high selectivity.
View Article and Find Full Text PDFJ Org Chem
November 2019
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, College of Chemistry , Northeast Normal University, Changchun 130024 , China.
We described a trifluoromethylation of alkenes using PhICFCl as bifunctional reagent. Chlorotrifluoromethylated products were obtained when nonconjugated alkenes were treated with PhICFCl in 1,4-dioxane at 60 °C, while vinyl C-H trifluoromethylated products were obtained by further elimination of hydrochloride in the case of those conjugated alkene substrates in DMF. Broad substrate scope, especially including complex alkenes bearing biological active motifs, suggests that this mild reaction is feasible for late-stage modification in drug discovery.
View Article and Find Full Text PDFJ Org Chem
June 2019
School of Chemistry & Chemical Engineering , Yangzhou University, Yangzhou 225005 , China.
Described herein is a visible-light-driven chlorotrifluoromethylative and chlorotrichloromethylative cyclization reaction to synthesize chlorotrifluoromethylated and chlorotrichloromethylated cyclic compounds. Visible-light photochemistry was utilized to generate trifluoromethyl and trichloromethyl radicals and trigger radical addition/cyclization/chlorination sequences. The use of terminal alkene-derived enynes enables the regioselective and stereoselective synthesis of chlorotrifluoromethylated and chlorotrichloromethylated pyrrolidines, piperidines, and cyclopentanes.
View Article and Find Full Text PDFChemistry
August 2018
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853, USA.
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!