Esters and N,N-dialkylamides of 2-(trifluoromethyl)acrylic acid (TFMAA) through Pd-catalysed carbonylation of fluorinated unsaturated substrates

Aminocarbonylation of phenylacetylene catalysed by palladium acetate in combination with (2-pyridyl)diphenylphosphine and methanesulfonic acid

“…Our interest in the synthesis of ␣,␤-unsaturated amides, in particular the ones deriving from 2-arylpropenoic acids (Scheme 1, R = aryl) [4] and our concern in the use of alkyne carbonylation for the synthesis of valuable fine chemicals [5] spurred us to explore the feasibility of phenylacetylene carbonylation in the presence of amines.…”

Alkoxycarbonylation of 3,3,3-Trifluoropropyne: an Intriguing Reaction to Prepare Trifluoromethyl-Substituted Unsaturated Acid Derivatives

“…Comparing the data in Table 1 with those obtained using 2-pyridyldiphenylphosphine under analogous conditions [5] it appears that, while the new ligand affords lower reaction rates, it allows one to obtain higher regioselectivities towards 1.…”

“…Analytical and spectroscopic data for 1, 2 and 4 have been reported elsewhere, [5] we report here the mass spectrum of …”

“…In a recent study, [5] we have shown that, when the carbonylation of 3,3,3-trifluoropropyne is carried out using as catalyst Pd(OAc) 2 in combination with 2-pyridyldiphenylphosphine and methanesulfonic acid (Drent×s catalytic system [6,7] ), it is possible to adjust the reaction conditions in order to enhance either the activity of the catalyst or the regioselectivity of the reaction. These intriguing preliminary results, and our interest in the development of a practical synthesis of new coatings for cultural heritage, prompted us to investigate the possibility of further improve the efficiency of our synthetic approach by using more active and selective ligands such as (6-methylpyrid-2-yl)diphenylphosphine.…”

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.…”