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.
Protic Acid Immobilized on Solid Support as an Extremely Efficient
Recyclable Catalyst System for a Direct and Atom Economical Esterification of
Carboxylic Acids with Alcohols
A. K. Chakraborti, B. Singh, S. V. Chankeshwara, A. R. Patel, J. Org. Chem., 2009,
74, 5967-5974.
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,
2479-2482.
Carboxylic acid esters can be prepared in very good yields at room temperature
from an acid and either a phenol or an aliphatic alcohol using the peptide
coupling reagents TBTU, TATU, or COMU, in the presence of organic bases.
Reactions using TBTU and TATU are faster but do not occur with tertiary
alcohols. Selective monoesterifications of diols and polyols can be achieved
with choice of base and coupling agent.
J. K. Twibanire, T. B. Grindley, Org. Lett., 2011,
13, 2988-2991.
Imidazole carbamates and ureas are chemoselective esterification and amidation
reagents. A simple synthetic procedure allows the conversion of a wide variety
of carboxylic acids to ester or amide analogues in high yields.
S. T. Heller, R. Sarpong, Org. Lett., 2010,
12, 4572-4575.
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.
