Editors' Choice—Highly Diastereoselective Anodic Fluorination of Organosulfur Compounds Based on Neighboring Participation. Issue 10 (21st June 2019)

• Record Type: Journal Article
• Authors: Furuta, Shoji; Inagi, Shinsuke; Fuchigami, Toshio
• Is Part Of: Journal of the Electrochemical Society. Volume 166:Issue 10(2019)
• Page Start: G110
• Page End: G115
• Publication Date: 2019-06-21
• Subjects: Electrosynthesis -- Organic Electrochemistry -- diastereoselective anodic substitution -- electrochemical fluorination -- neighbouring group participation; Electrochemistry -- Periodicals; 541.3705
• DOI: 10.1149/2.1331910jes
• Languages: English
• ISSNs: 0013-4651

Abstract

Abstract : Highly diastereoselective and efficient anodic α-fluorination of phenyl, p -chlorophenyl, and 2-naphthyl 3, 3, 3-trifluoro-2-methoxypropyl sulfides was successfully carried out at platinum electrodes in Et3 N-nHF (n = 3–5)/MeCN to provide the corresponding α-fluorinated products in good yields, whereas the corresponding p -methoxyphenyl sulfide derivative gave much lower diastereoselectivity. On the basis of such marked substituent effects on the diastereoselectivity and a previous study of anodic methoxylation of related sulfides, as well as the X-ray analysis of the configuration of the major diastereomer of the electrochemically fluorinated β -naphthyl derivative, it was clarified that the high diastereoselectivity is attributable to the neighboring MeO group participation to the anodically generated cationic intermediate destabilized by an electron-withdrawing CF3 group.