Categories: C-O Bond Formation > Synthesis of esters >
Oxidative Esterification
Name Reactions
Recent Literature
A one-pot conversion of aldehydes to esters interfaces
N-heterocyclic carbene-based organocatalysis with electro-organic synthesis to
achieve direct oxidation of catalytically generated electroactive intermediates.
A broad range of aldehyde and alcohol substrates has been converted. Furthermore,
the anodic oxidation reactions are very clean, producing only H2 gas
as a result of cathodic reduction.
E. E. Finney, K. A. Ogawa, A. J. Boydston, J. Am. Chem. Soc., 2012,
134, 12374-12377.
N-Heterocyclic carbenes catalyze the oxidation of unactivated aldehydes to
esters with manganese(IV) oxide in excellent yield under mild conditions. The reaction proceeds
through a transient activated alcohol generated in situ and
preserves stereochemical integrity. Various esters can be
synthesized using a broad range of alcohols and unactivated
aldehydes.
B. E. Marki, K. A. Scheidt, Org. Lett.,
2008,
10, 4331-4334.
VO(acac)2 catalyzes the oxidation of aromatic and aliphatic aldehydes
to the corresponding acids efficiently and selectively in the presence of
hydrogen peroxide as an oxidant. This method offers functional-group
compatibility, easy workup procedure, and a short reaction time. The performance
of titania-supported VO(acac)2 in the oxidation of aldehydes was also
investigated.
D. Talukdar, K. Sharma, S. K. Bharadwaj, A. J. Thakur, Synlett, 2013, 24,
963-966.
An efficient N-heterocyclic carbene (NHC)-mediated oxidative
esterification of aldehydes in an undivided microfluidic electrolysis cell
provides up to 4.3 g h-1 of product in a single pass with excellent
yields at ambient temperature. The oxidative acylation reactions proceed with a
1:1 stoichiometry of aldehyde and alcohol (for primary alcohols) with remarkably
short residence times in the electrolysis cell (<13 s) without electrolyte.
R. A. Green, D. Pletcher, S. G. Leach, R. C. D. Brown, Org. Lett.,
2015,
17, 3290-3293.
A simple, efficient, and high-yield procedure for the oxidative conversion of
alcohols to various types of esters and ketones was successfully carried out
with molecular iodine as the oxidant and potassium carbonate.
N. Mori, H. Togo, Tetrahedron, 2005,
61, 5915-5925.
Highly efficient, mild, and simple protocols allow the oxidation of aldehydes to
carboxylic acids and esters utilizing Oxone as the sole oxidant. These reactions
may prove to be valuable alternatives to traditional metal-mediated oxidations.
B. R. Travis, M. Sivakumar, G. O. Hollist, B. Borhan, Org. Lett., 2003,
5, 1031-1034.
In a mild and efficient oxidative esterification using TCCA as the oxidant,
aromatic and aliphatic aldehydes are converted in situ into their corresponding
acyl chlorides, which are then reacted with primary and secondary aliphatic,
benzylic, allylic, and propargylic alcohols and phenols to give various esters
in high yields.
S. Gaspa, A. Porcheddu, L. De Luca, Org. Lett.,
2015,
17, 3666-3669.
A highly effective synthesis of methyl esters from benzylic alcohols, aldehydes,
or acids via copper-catalyzed C-C cleavage from tert-butyl hydroperoxide
is easily accessible and practical and offers an alternative to the traditional
way.
Y. Zhu, H. Yan, L. Lu, D. Liu, G. Rong, J. Mao, J. Org. Chem., 2013,
78, 9898-9905.
Cooperative carbene catalysis allows selective oxidative acylations of alcohols
with aldehydes even in the presence of amino groups by using a readily available
cheap organic oxidant. Quantum chemical calculations support the suggested
mechanism.
S. De Sarkar, S. Grimme, A. Studer, J. Am. Chem. Soc., 2010,
132, 1190-1191.
Oxidative methyl esterification of primary alcohols and diols with methanol in
the presence of acetone as a hydrogen acceptor was successfully achieved under
catalysis of an iridium complex combined with 2-(methylamino)ethanol (MAE).
N. Yamamoto, Y. Obora, Y. Ishii, J. Org. Chem., 2011,
76, 2937-2941.
Screening of simple binary and ternary admixtures of Pd/charcoal in combination
with one or two metal and/or metalloid components as the catalyst for aerobic
oxidative methyl esterification of primary alcohols revealed two very effective
catalyst compositions. One was used in batch aerobic oxidation reactions,
whereas the other achieved nearly 60 000 turnovers in a continuous-flow
packed-bed reactor with no apparent loss of catalytic activity.
D. S. Mannel, M. S. Ahmed, T. W. Root, S. S. Stahl, J. Am. Chem. Soc., 2017,
139, 1690-1698.
A readily accessible catalyst system consisting of Pd/charcoal in combination
with bismuth(III) nitrate and tellurium metal enables an efficient aerobic
oxidative methyl esterification of primary alcohols, exhibits a broad substrate
scope, and is effective with both activated and unactivated alcohols bearing
diverse functional groups. The Bi and Te additives significantly increase the
reaction rate, selectivity, and overall product yields.
A. B. Powell, S. S. Stahl, Org. Lett., 2013,
15, 5072-5075.
Alcohols and aldehydes can be oxidized to the corresponding methyl esters by
reaction with methanol in the presence of crotononitrile as a hydrogen acceptor
using a catalyst combination of Ru(PPh3)3(CO)H2
with xantphos.
N. A. Owston, T. D. Nixon, A. J. Parker, M. K. Whittlesey, J. M. J. Williams, Synthesis, 2009,
1459-1462.
N. A. Owston, T. D. Nixon, A. J. Parker, M. K. Whittlesey, J. M. J. Williams,
Synthesis, 2009, 1459-1462.
Aldehydes and siloxanes form methyl esters in a single step through mild
oxidative esterification in the presence of a palladium catalyst or,
alternatively, afford secondary alcohols via TBAF-promoted arylation in the
absence of a catalyst at increased temperatures.
R. Lerebours, C. Wolf, J. Am. Chem. Soc., 2006,
128, 13052-13053.
Aldehydes undergo oxidative transformation to the methyl esters in methanol
as solvent upon treatment with catalytic amounts of vanadium pentoxide in
combination with hydrogen peroxide. This method features mild reaction conditions,
short reaction times, high efficiencies, cost-effectiveness, and facile
isolation of the desired products.
R. Gopinath, B. Patel, Org. Lett., 2000, 2, 577-579.
N-Heterocyclic carbenes catalyze the oxidation of various allylic, propargylic,
and benzylic alcohols to esters with manganese(IV) oxide in excellent yields.
Saturated esters can also be accessed from aldehydes using this method. A
desymmetration of meso-1,2-diols using a chiral catalyst is described.
B. E. Maki, A. Chan, E. M. Phillips, K. A. Scheidt, Org. Lett., 2007,
9, 371-374.
Copper(II) catalyzes a cross dehydrogenative coupling (CDC) reaction of
aldehydes with alkylbenzenes in the presence of TBHP to yield benzylic esters.
S. K. Rout, S. Guin, K. K. Ghara, A. Banerjee, B. K. Patel, Org. Lett., 2012,
14, 3982-3985.
A copper-catalyzed cross-dehydrogenative coupling reaction between N-hydroxyphthalimide and aldehydes using PhI(OAc)2 as an oxidant
enables a synthesis of NHPI esters in good yields in water. This facile and
efficient method is eco-friendly and offers mild conditions,
short reaction time, and broad substrate scope.
Z. Guo, X. Jiang, C. Jin, J. Zhou, B. Sun, W. Su,
Synlett, 2017, 28, 1321-1326.
An efficient iodine-mediated oxidative esterification of acetophenones provides
various α-ketoesters and esters in high yields in the presence of potassium
xanthates. The potassium xanthate not only promotes oxidative esterification but
also provides an alkoxy moiety for the reaction.
X. Luo, R. He, Q. Liu, Y. Gao, J. Li, X. Chen, Z. Zhu, Y. Huang, Y. Li, J. Org. Chem., 2020, 85,
5220-5230.
Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols
using molecular oxygen gives a broad range of α-ketoesters in good yields.
Mechanism studies evealed that the carbonyl oxygen in the ester mainly
originated from dioxygen.
X. Xu, W. Ding, Y. Lin, Q. Song, Org. Lett.,
2015,
17, 516-519.
An enantioselective synthesis of γ-nitroesters by a one-pot asymmetric Michael
addition/oxidative esterification of α,β-unsaturated aldehydes is based on an
enantioselective organocatalytic nitroalkane addition followed by an N-bromosuccinimide-based
oxidation. The γ-nitroesters are obtained in good yields and
enantioselectivities, and the method provides an attractive entry to optically
active γ-aminoesters, 2-piperidones, and 2-pyrrolidones.
K. L. Jensen, P. H. Poulsen, B. S. Donslund, F. Morana, K. A. Jørgensen, Org. Lett., 2012,
14, 1516-1519.