Categories: C-O Bond Formation > Synthesis of esters > Esterification, Transesterification, Acylation >

Esterifications

Name Reactions

Recent Literature

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, the recovery and reuse of commercially available polystyrene-supported DMAP was achieved without using any solvents.
A. Sakakura, K. Kawajiri, T. Ohkubo, Y. Kosugi, K. Ishihara, J. Am. Chem. Soc., 2007, 129, 14775-14779.

The reaction between carboxylic acids and dialkyl dicarbonates, in the presence of a weak Lewis acid such as magnesium chloride and the corresponding alcohol as the solvent, leads to esters in excellent yields. The mechanism involves a double addition of the acid to the dicarbonate, affording a carboxylic anhydride and CO₂.
G. Bartoli, M. Bosco, A. Carlone, R. Dalpozzo, E. Marcantoni, P. Melchiorre, L. Sambri, Synthesis, 2007, 3489-3496.

Borane-tetrahydrofuran complex or borane-methyl sulfide complex is used to generate triacyloxyboranes, which can be effectively reacted with various nucleophiles (alkylamines, arylamines, hydrazides, alcohols, phenols) at reflux in toluene to provide the corresponding amides and esters in excellent yield.
Z. Huang, J. R. Reilly, R. N. Buckle, Synlett, 2007, 1026-1030.

Silica chloride is an efficient catalyst for esterification of carboxylic acids with alcohols as well as for transesterification of esters by both alcoholysis and acidolysis.
K. V. N. S. Srinivas, I. Mahender, B. Das, Synthesis, 2003, 2390-2394.

Cobalt(II) chloride hexahydrate efficiently catalyzes the acetylation of alcohols with AcOH in high yields without the need to remove water. This protocol is also effective with other carboxylic acids. The catalyst can be recycled.
S. Velusamy, S. Borpuzari, T. Punniyamurthy, Tetrahedron, 2005, 61, 2011-2015.

A new facile method for selective monoesterification of diols - in particular oligoethylene glycols - has been developed. The reaction of diols with aromatic and aliphatic acids in presence of Al₂O₃ and MeSO₃H gave monoesterified products in excellent yields without use of any solvents.
H. Sharghi, M. Hosseini Sarvari, Tetrahedron, 2003, 59, 3627-3633.

A convenient procedure allows the synthesis of esters and thioesters from the corresponding carboxylic acid using TFFH as the coupling reagent. The preparation of N-acyl-dithiocarbamates from carboxylic acids and 1,3-thiazolidine-2-thione is also described.
M. Pittelkow, F. S. Kamounah, U. Boas, B. Pedersen, J. B. Christensen, Synthesis, 2004, 2485-2492.

The data of a study on mixed aliphatic-aromatic anhydrides suggest that during the Yamaguchi esterification reaction, a symmetric aliphatic anhydride is produced in situ, which upon reaction with an alcohol yields the ester. A one-pot procedure for the regioselective synthesis of aliphatic esters is described using benzoyl or p-toluoyl chloride instead of the sterically hindered Yamaguchi acid chloride.
I. Dhimitruka, J. SantaLucia, Org. Lett., 2006, 8, 47-50.