Facile syntheses of various per- or polyfluoroalkylated internal acetylene derivatives

Highly stereoselective one-pot synthesis of tetrasubstituted alkenes via carbopalladation reaction of fluorine-containing acetylene derivatives

“…Initially, the reaction of trifluoromethylated internal alkyne 2a [10] with iodobenzene and phenylboronic acid in the presence of palladium catalyst was examined (Table 1) [11]. Thus, treatment of 2a with 2.0 equiv.…”

“…Thin layer chromatography (TLC) was done with Merck silica gel 60 F 254 plates and column chromatography was carried out with Wako gel C-200. All acetylenes were prepared according to the previous literature procedure [10].…”

Highly regio- and stereoselective hydrosilylation of β-fluoroalkylated α,β-unsaturated ketones

“…Yield 62%; Yellow liquid; IR (neat) 3408, 1683,1611,1514,1466,1305,1254,1176,1121,1080,1034,977,834 6.10 (ddq, J = 15.59, 2.00, 6.79 Hz, 1H), 6.59 (ddq, J = 15.59, 4.00, 2.00 Hz, 1H), 6.36-6.38 (m, 1H), 6.57-6.62 (m, 1H), 7.425-7.430 (m, 1H); 13 …”

“…cm À1 : HRMS (FAB) Calcd for (M + ) C 11 H 11 F 3 O 2 : 232.0711, Found 232.0705; 1 H NMR (CDCl 3 ) d = 2.31(m, 1H), 3.82 (s, 3H), 5.31 (m, 1H), 6.02-6.07 (m, 1H), 6.49-6.54 (m, 1H), 6.87-6.93 (m, 3H), 7.29-7.33 (m, 1H);13 C NMR (CDCl 3 ) d = 55.16-55.18 (m), 72.50-72.51 (m), 112.1, 113.4, 117.6 (q, J = 33.9 Hz), 118.7, 123.2 (q, J = 269.5 Hz), 130.0, 141.0 (q, J = 5.8 Hz), 142.2, 159.9; 19 F NMR (CDCl 3 , CFCl 3 ) d = À64.49 (d, J = 4.89 Hz, 3F).4.2.3. (E)-4,4,4-Trifluoro-1-(2-methoxyphenyl)-2-buten-1-ol (9F)Yield 69%; Yellow liquid; IR (neat)3411, 2955, 1681, 1603, 1489, 1457, 1266, 1117, 1046 19 F NMR (CDCl 3 , CFCl 3 ) d = À64.21 (d, J = 6.79 Hz, 3F).…”

The catalytic olefination reaction of aldehydes and ketones with CBr3CF3

“…This reagent can be used as the starting material for trifluoromethylated acetylenes [1], trifluoromethylated polyfunctionalized cyclopropanes [2], trifluoromethyl-substituted enamines [3], trifluoromethyl propargyl alcohols [4], fluorine-containing optically active allylic alcohols [5], alpha-(trifluoromethyl)styrenes [6], esters and amides of 2-(trifluoromethyl)acrylic acid [7]. These examples indicate that the combination of trifluoromethyl group and bromine in adjacent position of double bond is very synthetically useful and opens up synthetic possibilities.…”