Categories: C-O Bond Formation >
Synthesis of esters
Related: |
 |
 |
 |
 |
Reactions
Esterification, Transesterification, Acylation
Decarboxylative Esterification
Oxidative Esterification
Redox Esterification
Name Reactions
Passerini Reaction
|
Two Steps:
|
Protecting Groups
Benzyl esters
Recent Literature
Sulfuryl fluoride activates the carbonyl groups of amides as nucleophiles
while the activated hydroxyl groups of alcohols act as electrophiles. The amide
C-N bonds could be easily cleaved to form the ester C-O bonds at room
temperature without using transition metals. The reaction offers broad substrate
scope and excellent functional group compatibility.
W.-Y. Fang, G.-F. Zha, H.-L. Qin,
Org. Lett., 2019, 21, 8657-8661.
N-alkoxyamides conveniently afford the corresponding carboxylic esters in
the presence of NBS in toluene via oxidative homocoupling and the subsequent
thermal denitrogenation. Even substrates bearing a bulky or long-chain
substituent gave products in good yields in this convenient and economic
approach to a direct transformation of an alkoxyamide moiety into the carboxylic
ester functional group.
N. Zhang, R. Yang, D. Zhang-Negrerie, Y. Du, K. Zhao, J. Org. Chem., 2013,
78, 8705-8711.
In a Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C
bond cleavage, various common ketones, even inactive aryl long-chain alkyl
ketones, are selectively converted into esters. The reaction tolerates a wide
range of alcohols, including primary and secondary alcohols, chiral alcohols
with retention of the configuration and electron-deficient phenols.
X. Huang, X. Li, M. Zou, S. Song, C. Tang, Y. Yuan, N. Jiao,
J. Am. Chem. Soc., 2014,
136, 14858-14865.
A catalytic amount of ytterbium(III) triflate as a Lewis acid promoter
enables the conversion of a broad range of imides in the presence of alcohols,
water, amines, or N,O-dimethylhydroxylamine to the corresponding esters,
carboxylic acids, amides, and Weinreb amides in good yields.
C. Guissart, A. Barros, L. R. Barata, G. Evano, Org. Lett.,
2018, 20, 5090-5093.
A scalable electrochemical esterification between aroylhydrazides and
alcohols provides carboxylic esters with mild reaction conditions, a relatively
broad substrate scope, and good functional group compatibility. In addition, the
transformation is operationally simple and free from external oxidants and
additives.
P. Xie, X. Peng, P. Feng, Synthesis, 2023,
55, 3005-3012.
A one-carbon homologation of an alcohol to the extended carboxylic acid, ester,
or amide involves a Mitsunobu reaction with an alkoxymalononitrile, followed by
unmasking in the presence of a suitable nucleophile. The homologation and
unmasking can even be performed in a one-pot process in high yield.
N. Kagawa, A. E. Nibbs, V. H. Rawal, Org. Lett.,
2016, 18, 2363-2366.
In a Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles, acyl
electrophiles were in situ generated via chemoselective C(CO)-CN bond cleavage.
Alcohols, alkoxsilanes, silicate esters, or borate esters can be acylated to the
corresponding aryl esters in good to excellent yields under molecular oxygen.
Dioxygen serves as both oxidant and reactant.
W. Kong, B. Li, X. Xu, Q. Song, J. Org. Chem.,
2016, 81, 8436-8443.
The allylic oxidation of cyclic alkenes with a copper-aluminum mixed oxide as
catalyst in the presence of a carboxylic acid and tert-butyl
hydroperoxide as the oxidant gives the corresponding allylic esters. When
l-proline is employed, the allylic alcohol or ketone is obtained.
A. L. García-Cabeza, R. Marín-Barrios, F. J. Moreno-Dorado,
M. J. Ortega, G. M. Massanet, F. M. Guerra, Org. Lett., 2014,
16, 1598-1601
The facile and efficient conversion of a tert-butyl protecting group
to an acetyl protecting group by catalytic amounts of bromine in acetyl
chloride and the presence of acetic acid has been developed. The fairly mild reaction conditions are of particular interest for
new protecting group strategies for sulfur functionalised target structures.
A. Blaszczyk, M. Elbing, M. Mayor, Org. Biomol. Chem., 2004, 2,
2722-2724.
Group 5 and 6 metal chlorides were found as very efficient catalysts for
acylative cleavage of ethers. Compared with conventional Lewis acid
catalysts, group 5 and 6 metal chlorides showed better results in the
catalytic C-O bond cleavage.
Q. Guo, T. Miyaji, R. Hara, B. Shen, T. Takahashi, Tetrahedron, 2002, 58,
7327-7334.
A stereoconservative protection and deprotection method
of amino and carboxyl groups includes the generation of N-Phthaloyl N'-alkyl
secondary amides from N-phthaloyl amino acids by using a mixed anhydride method. These secondary
amides have been transformed by thermal rearrangement of the intermediate nitrosoamides
to esters with retention of configuration and excellent yields.
D. M. Shendage, R. Froehlich, G. Haufe, Org. Lett., 2004, 6,
3675-3678.