Facile synthesis of (β-chlorodifluoroethyl)phosphonates via chlorination reaction of difluoroalkyl diazo derivatives with HCl

Copper-catalyzed multicomponent reaction of β-trifluoromethyl β-diazo esters enabling the synthesis of β-trifluoromethyl N,N-diacyl-β-amino esters

“…In 2017, Zhang, Hu, and co-workers developed a Cu-catalyzed reaction of CF 3 CHN 2 with carboxylic acids and acetonitrile via a similar process to afford a series of N-trifluoroethylimides (Scheme 1b) [40,41]. Inspired by these elegant works [31][32][33][34][35][36][37][38][39][40][41] and based on our continuous interest in reactions of fluoroalkyldiazo compounds [42][43][44][45][46][47][48][49], we sought to develop reactions of the unexplored β-trifluoromethyl β-diazo esters. We hypothesized that nitrile ylides, in situ generated from nitriles and β-trifluoromethyl β-amino esters, could also react with carboxylic acids to give nitriliums, which then could undergo a Mumm rearrangement to provide unsymmetrical β-trifluoromethyl diacyl-β-amino esters as products (Scheme 1c).…”

Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups

“…As a part of our continuing investigations in fluorinated carbene chemistry [ 45 – 49 ], we hypothesized that the synthesis of cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups at the ring might be possible by using our newly developed bench-stable diazo reagent CF 3 C(N 2 )CF 2 P(O)(OEt) 2 . Therefore, we report herein our preliminary results toward this goal via copper iodide-catalyzed cyclopropanation reaction of an acceptor carbene precursor with selected terminal alkenes.…”

A Cu-promoted reaction of β-keto trifluoromethyl amines enabling stereoselective synthesis of trifluoromethylated aziridines

“…Based on our continuous interest in the synthesis of trifluoromethyl heterocycles 13 and reactions of trifluoromethylated β-amino carbonyl compounds and diazos, 14 we envision that direct ring closing of β-amino ketones might be accomplished to assemble trifluoromethylated free (NH)-aziridines. 15 Herein, we report an efficient method for the synthesis of trifluoromethylated NH-aziridines via a copper-promoted intramolecular cyclization reaction of trifluoromethylated β-keto amines (Scheme 1e).…”