PdII-catalyzed reaction of phenols with propiolic esters.: A single-step synthesis of coumarins

The intermolecular reaction of phenols with propiolic esters in TFA in the presence of a Pd(OAc)(2) catalyst, affording coumarin derivatives. is described. An exclusive formation of 5,6,7-trimethoxy-4-phenylcoumarin was observed in the reaction of 3,4.5-trimethoxyphenol and ethyl phenylpropiolate with a catalytic amount of Pd(OAc)(2). The reaction in the absence of Pd(OAc)(2) did not give any coumarin at all. Coumarin derivatives were obtained in high yields in the cases of electron-rich phenols, such as 3,4-methylenedioxyphenol, 3-methoxyphenol, 2-naphthol, and 3,5-dimethoxyphenol. Furthermore, the reaction of some phenols with various 2-alkynoates or with diethyl acetylenedicarboxylate gave the corresponding coumarins in good-to-high yields.