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.
Triphenylphosphine oxide catalyzes amidation and esterification for an
efficient synthesis of dipeptides, amides, and esters in good yields in less
than 10 m without racemization. This reaction is applicable to challenging
couplings of hindered carboxylic acids with weak nucleophiles amines or
alcohols.
J.-W. Ren, M.-N. Tong, Y.-F. Zhao, F. Ni, Org. Lett., 2021, 23,
7497-7502.
The coupling reagent ethyl 2-cyano-2-(2-nitrobenzenesulfonyloxyimino)acetate (o-NosylOXY)
produces only byproducts that can be easily recovered and reused for the
synthesis of the same reagent, making coupling reactions to yield amides,
hydroxamates, peptides, and esters more environmentally friendly and
cost-effective.
D. Dev, N. B. Palakurthy, K. Thalluri, J. Chandra, B. Mandal, J. Org. Chem., 2014,
79, 5420-5431.
Graphene oxide is an efficient and reusable acid catalyst for the esterification
reaction. A wide range of aliphatic and aromatic acids and alcohols were
compatible and afforded the corresponding products in good yields. The
heterogeneous catalyst can be easily recovered and recycled.
Z. Chen, Y. Wen, Y. Fu, H. Chen, M. Ye, G. Luo,
Synlett, 2017, 28, 981-985.
A macroporous polymeric acid catalyst enables a direct esterification of
carboxylic acids and alcohols at 50 to 80°C without removal of water to give the
corresponding esters with high yield. Flow esterification for the synthesis of
biodiesel fuel was also achieved by using a column-packed macroporous acid
catalyst under mild conditions.
M. Minakawa, H. Baek, Y. M. A. Yamada, J. W. Han, Y. Uozumi, Org. Lett., 2013,
15, 5798-5801.
Sulfuryl fluoride (SO2F2) mediates a dehydrative coupling
of carboxylic acids with alcohols at room temperature with high
efficiency. This method offers broad substrate scope, mild conditions, excellent
functional group compatibility and affords esters in high yields, even on gram
scale.
S.-M. Wang, N. S. Alharbi, H.-L. Qin, Synthesis, 2019, 51,
3901-3907.
A benzyne-mediated esterification of carboxylic acids and alcohols provides
products under mild conditions via a selective nucleophilic addition of
carboxylic acid to benzyne in the presence of alcohol followed by a
transesterification with alcohol. Benzyne can also be used to promote
lactonization and amidation reactions.
J. Zhao, J. Shi, Y. Li, Org. Lett., 2021, 23,
7274-7278.
A porous phenolsulfonic acid-formaldehyde (PSF) resin as solid-acid catalyst
shows excellent performance in the esterification of fatty acids without using
any solvent or introducing a water-removal process. The catalyst was reused up
to 30 times without significant loss of activity.
Y.-H. Kim, J. Han, B. Y. Jung, H. Baek, Y. M. A. Yamada, Y. Uozumi, Y.-S. Lee,
Synlett, 2016, 27, 29-32.
A convenient and efficient sonochemical method for methyl esterification of
carboxylic acids is catalyzed by polymer-supported triphenylphosphine in the
presence of 2,4,6-trichloro-1,3,5-triazine and Na2CO3.
Methyl esters of various carboxylic acids bearing reactive hydroxyl groups as
well as acid- or base-labile functionalities could be rapidly prepared within
short times in good to excellent yields in high purities without column
chromatography.
S. Jaita, W. Phakhodee, M. Pattarawarapan,
Synlett, 2015, 26, 2006-2008.
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.
An oxyma derivative, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl
2-cyano-2-(hydroxyimino)acetate, displayed a remarkable effect on selective
esterifications of primary alcohols. A wide range of carboxylic acids could be
esterified with primary alcohols by using EDCI, NaHCO3 in 5% H2O-CH3CN.
The Oxyma derivative can be removed after the reaction via a simple basic or an
acidic aqueous workup procedure.
Y. Wang, B. A. Aleiwi, Q. Wang, M. Kurosu, Org. Lett., 2012,
14, 4910-4913.
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.