Zum reaktionsverhalten funktionalisierter fluorolefine

Perfluoroalkylation with Organosilicon Reagents

“…Similar to 2 , ( n -C 3 H 7 ) 3 SiCFCF 2 undergoes formal insertion into the sulfur−oxygen bond of γ-SO 3 …”

“…Further, metalation of the olefinic C-H bond in the corresponding cis-or transsilane followed by trapping of the resulting carbanion species by tributyltin chloride or triethylsilyl chloride leads to the geometrically pure stannyl and silyl Similar to 2, (n-C 3 H 7 ) 3 SiCFdCF 2 undergoes formal insertion into the sulfur-oxygen bond of γ-SO 3 . 100 The product silyl ester is readily hydrolyzed to give polyfluorovinylated sulfonic acid and other valuable products.…”

Copper-Catalyzed Synthesis of Indol-3-yl α-(Difluoromethyl)-α-(trifluoromethyl)carbinols: Construction of Difluoromethylated sp3 Carbon Centers

“…For our initial studies (Table ), 1-methyl-1 H -indole ( 2a ) was used as the substrate in combination with 1,1,3,3,3-pentafluoro-2-trimethylsiloxypropene ( 1 ) as fluorinating reagent. , The use of CuI as catalyst and wet dichloroethane (DCE) as the solvent at 80 °C allowed the formation of carbinol 3a in 90% yield (entry 1). Gratifyingly, better yield was observed with other copper salts, such as CuBr, CuCl, CuCN, and CuSCN (entries 2–5).…”

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

“…Thus, the reactions of 174a and 174c with LiAlH 4 provide (Z)-1,2-difluorovinylsilanes 180[69] and 183[70], respectively (Scheme 45). The silyl group of 180 and 183 can be replaced with stannyl group[69] and iodine, respectively[70] so that the silylated vinyl carbon in 174 offers the reaction site not only for the reaction with electrophiles but also for the transition metal-catalyzed crosscoupling reactions via the corresponding stannanes 181 and 182, and iodide 184.The Pd-catalyzed cross-coupling reaction of the related stannane 186 with alkenyl iodide 187 is shown in Scheme 46[71].The a-fluoro-b-substituted g-unsaturated carboxylic acids 190 were synthesized via a diastereoselective Claisen rearrangement of allyl difluorovinyl ethers 189 which were prepared in situ from allyl alcohols 188 and trifluorovinylsilane 174d (Scheme 47) [72].Trifluorovinylsilane 174a undergoes cycloaddition with sulfur trioxide, providing 191 which is transformed to either trimethylsilyl ester 192[73] or ethyl ester 193[74] of 1…”