Categories: C-O Bond Formation > Synthesis of esters > Esterification, Transesterification, Acylation >
Transesterifications
Recent Literature
In the presence of a Zn-cluster catalyst, alcohols are efficiently converted
to the corresponding acetates in very good yields just by refluxing in EtOAc. The mild reaction
conditions enabled a selective acetylation of various functionalized alcohols
even in the presence of highly nucleophilic aliphatic amino groups.
T. Iwasaki, Y. Maegawa, Y. Hayashi, T. Ohshima, K. Mashima, Synlett, 2009,
1659-1663.
A catalytic transesterification is promoted by a tetranuclear zinc cluster. The
mild reaction conditions enabled the reactions of various functionalized
substrates to proceed in very good yield. A large-scale reaction under
solvent-free conditions offers high environmental and economical advantages.
T. Iwasaki, Y. Maegawa, Y. Hayashi, T. Ohshima, K. Mashima, J. Org. Chem., 2008,
73, 5147-5150.
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.
K. V. N. S. Srinivas, I. Mahender, B. Das, Synthesis, 2003, 2390-2394.
Sc(OTf)3 catalyses a direct transesterification of carboxylic esters
in boiling alcohols. Methyl, ethyl, isopropyl, and allyl esters were prepared
from various substrates in high yields. The application of microwave irradiation
led to significantly reduced reaction times.
N. Remme, K. Koschek, C. Schneider, Synlett, 2007,
491-493.
K2HPO4 is an efficient catalyst for transesterifications
to produce methyl esters. Various functional groups are tolerated under the mild
reaction conditions.
T. Shinada, M. Hamada, K. Miyoshi, M. Higahino, T. Umezawa, Y. Ohfune, Synlett, 2010,
2141-2145.
A mild, functional group tolerant palladium-catalyzed carbonylation of aryl
chlorides using atmospheric pressure of carbon monoxide allows the preparation
of phenyl esters, alkyl esters and carboxylic acids. Phenyl esters are shown to
be useful acylating agents, delivering libraries of carbonyl derivatives,
including alkyl, allyl and thioesters, under very mild conditions.
D. A. Watson, X. Fan, S. L. Buchwald, J. Org. Chem., 2008,
73, 7096-7101.
Various alcohols, amines and N-hydroxylamines gave corresponding
formylated adducts in high yields by treatment with 2,2,2-trifluoroethyl
formate (TFEF). Chemoselective formylation of a primary amine could be readily
achieved in the presence of an unprotected primary alcohol.
D. R. Hill, C.-N. Hsiao, R. Kurukulasuriya, S. Wittenberger, Org. Lett.,
2002, 4, 111-113.
Transesterification/acylation reactions of secondary alcohols are
efficiently catalyzed by N-Heterocyclic carbenes (NHC) at room
temperature.
R. Singh, R. M. Kissling, M.-A. Letellier, S. P. Nolan, J. Org. Chem., 2004,
69, 209-212.
In the presence of sodium acetate, the reaction between 2,2,6-trimethyl-4H-1,3-dioxin-4-one
and secondary or tertiary alcohols or primary or secondary amines could be
carried out in refluxing tetrahydrofuran. Under these much milder conditions,
side products were avoided, and β-keto esters and β-ketoamides were normally
obtained in quantitative yields.
V. Sridharan, M. Ruiz, J. C. Menéndez, Synthesis, 2010,
1053-1057.
Iodine catalyses a facile transesterification of β-ketoesters.
S. P. Chavan, R. R. Kale, K. Shivasankar, S. I. Chandake, S. B. Benjamin, Synthesis, 2003, 2695-2698.
