Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups

• Ita Hajdin,
• Romana Pajkert,
• Mira Keßler,
• Jianlin Han,
• Haibo Mei and
• Gerd-Volker Röschenthaler

Beilstein J. Org. Chem. 2023, 19, 541–549, doi:10.3762/bjoc.19.39

• good to very good yields. Keywords: alkenes; cyclopropanation; diazo compounds; difluoromethylphosphonate; DFT calculations; Introduction Cyclopropanes constitute a fascinating class of organic compounds due to their unique structure and bond properties [1]. However, their synthetic utility is

• ). In addition, few examples of difluoromethylphosphonate containing cyclopropanes have been reported to date. These compounds were synthesized either by cyclopropanation of CF2P(O)(OEt)2-containing alkenoates using a Corey–Chaykovsky reagent (sulfaniumyl or oxosulfaniumyl methanides) and diazomethane

• or by photolysis of pyrazolines bearing difluoromethylphosphonate moieties (Scheme 1C) [35][36][37][38]. Notably, among the various CF2-containing functionalities, difluoromethylphosphonates represent a distinct class of compounds whose potential as nonhydrolyzable phosphate mimics is unquestionable

Copper-based fluorinated reagents for the synthesis of CF₂R-containing molecules (R ≠ F)

• Louise Ruyet and
• Tatiana Besset

Beilstein J. Org. Chem. 2020, 16, 1051–1065, doi:10.3762/bjoc.16.92

• -generated copper-based CF2PO(OEt)2 reagent As a bioisostere of the phosphonate group [47], a lot of attention was paid to the difluoromethylphosphonate residue as well as the development of efficient methodologies to introduce it onto molecules [48]. In that context, main contributions were made by the

• groups of Poisson and Goossen. In the course of their study regarding the synthesis of difluoromethylphosphonate-containing molecules, Poisson and co-workers investigated the in situ generation of a CuCF2PO(OEt)2 species and its application to functionalize various classes of compounds [49][50][51][52

• difluoromethylation of heteroarenes. Synthesis of difluoromethylphosphonate-containing molecules using the in situ-generated CuCF2PO(OEt)2 species. Synthesis of difluoromethylphosphonate-containing molecules using in situ-generated CuCF2PO(OEt)2 species with 1,10-phenantroline as a ligand. Phen: 1,10-phenanthroline