With regard to atom economy and E-factor, catalytic condensation of carboxylic acids with equimolar amounts of alcohols is the most desirable. Although several highly active dehydration catalysts have been reported, more efficient alternatives are still strongly needed because the dehydrative esterification of tertiary alcohols, phenols, acid-sensitive alcohols, amino acids, and hardly soluble alcohols has never proceeded satisfactorily. Here we report new insights into the classical DMAP-catalyzed acylation of alcohols: surprisingly, only a 0.05-2 mol % of DMAP can efficiently promote acylation of alcohols with acid anhydrides under auxiliary base- and solvent-free conditions to give the corresponding esters in high yields. Furthermore, we achieved the recovery and reuse of commercially available polystyrene-supported DMAP without using any solvents. These serendipitous findings provide widely useful and environmentally benign esterification methods, which might be more practical and reliable than catalytic dehydrative condensation methods, in particular, for the less reactive alcohols which hardly condense with carboxylic acid directly.

Brønsted base-assisted boronic acid catalysis for the dehydrative self-condensation of carboxylic acids is described. Arylboronic acid bearing bulky (N,N-dialkylamino)methyl groups at the 2,6-positions can catalyze the intramolecular dehydrative condensation of di- and tetracarboxylic acids. This is the first successful method for the catalytic dehydrative self-condensation of carboxylic acids.

Bifunctional Brønsted base-assisted boronic acid catalysts, arylboronic acids bearing two sterically bulky (N,N-dialkylamino)methyl groups at the 2,6-positions, exhibit remarkable activities for the dehydrative intramolecular condensation of dicarboxylic acids. The steric bulkiness of the (N,N-dialkylamino)methyl groups of 1, which prevents the formation of less active species such as the N→B chelated species and triarylboroxines 3, is crucial for the high catalytic activity. This is the first successful method for the catalytic dehydrative self-condensation of di- and tetracarboxylic acids.