One-pot esters synthesis from secondary alcohols and CO catalyzed byPd-phosphine systems

Abstract

The aim of the work is to develop the esters syntheses by combining in one reactor the acid–catalytic intramolecular alcohols dehydration and the resulting alkenes alkoxycarbonylation. Esters were synthesized from cycloalkanols or secondary alkanols C5–C9 and CO under mild conditions. For the first time, a wide range of catalytic systems including palladium precursor, organophosphine, strong protonic acid, and additive for binding water have been tested in the model one-pot process based on cyclohexanol and CO. For the first time, the dehydration processes of secondary linear alcohols C6, C7 and C9 were combined in one reactor with isomerizing alkoxycarbonylation catalyzed by Pd-systems with the XANTPHOS promoter. These processes led to the isomeric esters formation, among which 60–73% were linear carboxylic acid esters as products of terminal CO addition to alkenes.