Two-step conversion of carboxylic esters into distally fluorinated ketones via ring cleavage of cyclopropanol intermediates: Application of sulfinate salts as fluoroalkylating reagents

Yulia A. Konik, Marina Kudrjashova, Nele Konrad, Sandra Kaabel, Ivar Järving, Margus Lopp, Dzmitry G. Kananovich*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

30 Citations (Scopus)

Abstract

Tertiary cyclopropanols easily available from carboxylic esters have been used in the synthesis of distally fluorinated ketones. Cyclopropane ring cleavage reactions in methanol with aqueous tert-butyl hydroperoxide in the presence of a copper(ii) acetate catalyst and sodium triflinate (Langlois reagent) afford β-trifluoromethyl ketones in 16-74% isolated yields. Sodium triflinate serves as a precursor of reactive trifluoromethyl copper species, enabling ring-opening trifluoromethylation, as evidenced by mechanistic studies. We also demonstrate here that other sulfinate salts, such as sodium 1,1-difluoroethanesulfinate, sodium 2-(4-bromophenyl)-1,1-difluoroethanesulfinate and sodium 1-(trifluoromethyl)cyclopropanesulfinate, can be used as fluoroalkylation reagents, resulting in the corresponding fluorinated ketones.

Original languageEnglish
Pages (from-to)4635-4643
Number of pages9
JournalORGANIC AND BIOMOLECULAR CHEMISTRY
Volume15
Issue number21
DOIs
Publication statusPublished - 2017
MoE publication typeA1 Journal article-refereed

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