Categories: C-O Bond Formation > Synthesis of esters >
Oxidative Esterification
Name Reactions
Recent Literature
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.
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.
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.
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.
