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