| Title: | Synthesis of Selectively gem-Difluorinated Molecules; Chiral gem-Difluorocyclopropanes via Chemo-Enzymatic Reaction and gem-Difluorinated Compounds via Radical Reaction |
| Author(s): | Itoh T; Hayase S; Nokami T; |
| Address: | "Toyota Physical and Chemical Research Institute, Emeritus Professor of Tottori University, 41-1 Yokomichi, 480-1192, Nagakute city, Aichi, Japan. Department of Chemistry and Biotechnology, Tottori University, 4-101 Koyama-minami, 680-8552, Tottori, Japan. Department of Chemistry and Biotechnology, Center for Research on Green Sustainable Chemistry, Tottori University, 4-101 Koyama-minami, 680-8552, Tottori, Japan" |
| ISSN/ISBN: | 1528-0691 (Electronic) 1528-0691 (Linking) |
| Abstract: | "The incorporation of fluorine atoms into an organic compound can alter the chemical reactivity or biological activity of the resulting compound due to the strong electron withdrawing nature of the fluorine atom. We have synthesized many original gem-difluorinated compounds and described the results in four sections. The first section describes the synthesis of optically active-gem-difluorocyclopropanes via the chemo-enzymatic reaction; we applied these compounds to liquid crystalline molecules, then further discovered a potent DNA cleavage activity for the gem-difluorocyclopropane derivatives. The second section describes the synthesis of selectively gem-difluorinated compounds via a radical reaction; we synthesized fluorinated analogues of a sex pheromone of the male African sugarcane borer, Eldana saccharina, and used the compounds as proof for investigating the origin of pheromone molecule recognition on the receptor protein. The third involves the synthesis of 2,2-difluorinated-esters by visible light-driven radical addition of 2,2-difluoroacetate with alkenes or alkynes in the presence of an organic pigment. The last section describes the synthesis of gem-difluorinated compounds via the ring-opening of gem-difluorocyclopropanes. We further developed a novel method of synthesizing gem-difluorohomoallylic alcohols via the ring-opening of gem-difluorocyclopropane and aerobic oxidation by photo-irradiation in the presence of an organic pigment. Since gem-difluorinated compounds that were prepared by the present method have two olefinic moieties with a different reactivity at the terminal position, we accomplished the synthesis of four types of gem-difluorinated cyclic alkenols via the ring-closing-metathesis (RCM) reaction" |
| Keywords: | Radical reaction Ring closing metathesis Ring-opening Visible light gem-Difluorocyclopropane gem-Difluoromethylene; |
| Notes: | "PubMed-not-MEDLINEItoh, Toshiyuki Hayase, Shuichi Nokami, Toshiki eng JSPS Kakenhi/ Review 2023/03/23 Chem Rec. 2023 Sep; 23(9):e202300028. doi: 10.1002/tcr.202300028. Epub 2023 Mar 22" |
