Fluorinated acrylates via alkoxycarbonylation of 1-alkynes with fluorinated alcohols

Abstract The system formed by combining in situ Pd(OAc) 2 with (2-pyridyl)diphenylphosphine (PyPPh 2 ) and CH 3 SO 3 H catalyzes efficiently the carbonylation of terminal alkynes (phenylacetylene or 1-hexyne) with alcohols having perfluorinated segments of the type CF 3 (CF 2 ) m (CH 2 ) n –OH ( m =1 or 3, n =1, 2 or 3) or with pentafluorophenol. Good carbonylation rates accompanied by high regioselectivity towards acrylate ester formation are obtained under mild reaction conditions ( T =60–80 °C, P (CO)=30 atm). The influence of the CO pressure, the catalyst composition, the temperature and the number ( n ) of protonated methylene groups on the catalysis has been studied.