An Improved Method for SN2-Type Demethoxycarbonylation of Activated Esters with 4-Aminothiophenol and a Cesium Catalyst

Article abstract of DOI:10.1021/jo00366a017

A powerful method for demethoxycarbonylation of activated methyl esters was developed, employing stoichiometric amounts of 4-aminothiophenol and catalytic quantities of cesium carbonate in hot (85 deg C) DMF.The superiority of this technique over several others methods was demonstrated in a comparative study on linear polyprenoid substrates, in which the thiolate/Cs2CO3 approach benefited from shorter reaction times, lower temperatures, higher yields, and simpler workup procedures.The method unabled simultaneous removal of two methoxycarbonyl functions contained in a single molecule, a transformation representing a crucial step in the total synthesis of ubiquinone-10.