Electrochemical Properties and Fluorination of Cyclopropane Derivatives Bearing Arylthio Groups

Abstract

Electrochemical analyses of phenylthiocyclopropane derivatives and bis(arylthio)cyclopropanes were comparatively studied by cyclic voltammetric measurements. Based on the substituent effects on their oxidation potentials, a cyclopropane ring was confirmed to have a double bond system as reported. Anodic fluorination of phenylthiocyclopropanes resulted in the formation of sulfoxide and/or ring opening fluorinated products while 1,1-bis(arylthio)cyclopropanes afforded mainly desulfurizative monofluorinated cyclopropanes and sulfoxides together with ring opening fluorinated products. This is the first successful electrochemical fluorination of a cyclopropane ring.

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

“…The anodic fluorination of arylcyclopropane derivatives was reported recently [46,47], difluorinated or oxyfluorinated products were obtained [47]. Notably, anodic fluorination of cyclopropane derivatives bearing arylthio groups gives rise to a variety of possible reaction paths yielding monofluorinated sulfoxides as well as ring-opened fluorinated products [46]. Thus, recent publications on the topic concern only anodic opening of a cyclopropane ring followed by further functionalization of the carbon skeleton, demonstrating great synthetic potential of the process.…”

“…Quite recently, two publications from the Werz group appeared concerning anodic activation of donor-acceptor cyclopropanes followed by their functionalization with arenes [43] or yielding oxy-ketones or 1,2-dioxanes [44]; the latter process was inspired by a previous report of Buriez [45]. The anodic fluorination of arylcyclopropane derivatives was reported recently [46,47], difluorinated or oxyfluorinated products were obtained [47]. Notably, anodic fluorination of cyclopropane derivatives bearing arylthio groups gives rise to a variety of possible reaction paths yielding monofluorinated sulfoxides as well as ring-opened fluorinated products [46].…”

Electrochemical Fluorination of Dithiocarbonates Using a Triarylamine Mediator

“…In contrast to well‐established electrochemical perfluorination, selective electrochemical fluorination under safe conditions is still one of important subjects of modern organofluorine chemistry. Therefore, we have developed various electrochemical systems for selective fluorination of organic molecules and macromolecules, and systematically studied selective electrochemical fluorination of various heteroatom compounds and heterocycles so far [6–9].…”

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

“…Anodic fluorination of arylcyclopropane derivatives were reported recently [46,47], difluorination or oxyfluorination products were obtained [47]. Notably, anodic fluorination of cyclopropane derivatives bearing arylthio groups gives rise to a variety of possible reaction paths yielding monofluorinated sulfoxides as well as ring-open fluorinated products [46]. Thus, recent publications in the topic concern only anodic opening of a cyclopropane ring followed by further functionalization of the carbon skeleton, demonstrating great synthetic potential of the process.…”

“…Quite recently, two publications from Kolb group appeared concerning anodic activation of donor-acceptor cyclopropanes followed by their functionalization with arenes [43] or yielding oxy-ketones or 1,2-dioxanes formation [44]; the latter process was inspired by previous report of Buriez [45]. Anodic fluorination of arylcyclopropane derivatives were reported recently [46,47], difluorination or oxyfluorination products were obtained [47]. Notably, anodic fluorination of cyclopropane derivatives bearing arylthio groups gives rise to a variety of possible reaction paths yielding monofluorinated sulfoxides as well as ring-open fluorinated products [46].…”