Fluorinated acrylates via alkoxycarbonylation of 1-alkynes with fluorinated alcohols

The system formed by combining in situ Pd(OAc)2 with (2-pyridyl)diphenylphosphine (PyPPh2) and CH3SO3H catalyzes efficiently the carbonylation of terminal alkynes (phenylacetylene or 1-hexyne) with alcohols having perfluorinated segments of the type CF3(CF2)m(CH2)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.