Categories: C=O Bond Formation > Synthesis of carboxylic acids >
Synthesis of carboxylic acids by oxidation of alkenes
Name Reactions
Recent Literature
The OsO4-catalyzed direct oxidation of olefins via the
carbon-carbon cleavage of an osmate ester by the action of oxone allows the
preparation of ketones or carboxylic acids in high yields. This method
should be applicable as an alternative to ozonolysis.
B. R. Travis, R. S. Narayan, B. Borhan, J. Am. Chem. Soc., 2002, 124, 3824-3825.
Oxidative cleavage of various olefins to the corresponding ketones/carboxylic
acids occurs with catalytic amounts of 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)
and oxone as terminal oxidant in acetonitrile-water mixture at rt. The reaction
mechanism involves dihydroxylation of the olefin with oxone, oxidative cleavage
by TetMe-IBX, and oxidation of the aldehyde functionality to the corresponding
acid with oxone.
J. N. Moorthy, K. N. Parida, J. Org. Chem.,
2014,
79, 11431-11439.
A mild one-pot ozonolysis-oxidation process enables the synthesis of carboxylic
acids from alkenes. Conducting the ozonolysis in an aqueous organic solvent
eliminates secondary ozonide formation and the intermediates generated are
readily converted into a carboxylic acid by adding sodium chlorite. The desired
acids are isolated in high purity and high yield by simple extraction after a
reductive quench.
B. M. Cochran,
Synlett, 2016, 27, 245-248.
A catalytic amount of a composite material, RuO2/BaTi4O9,
in combination with NaIO4 in EtOAc-H2O has been shown to
efficiently cleave alkenes, affording ketones, aldehydes and/or carboxylic acids
in high yields.
H. Okumoto, K. Ohtsuko, S. Banjoya, Synlett, 2007,
3201-3205.
The combination of 1,2-dibutoxyethane/O2 enables an effective and
green oxidative cleavage of olefins to carboxylic acids in very good yields.
This oxidation system offers excellent functional-group tolerance, is applicable
for large-scale synthesis, and works without an external initiator, catalyst, or
additive.
J. Ou, H. Tan, S. He, W. Wang, B. Hu, G. Yu, K. Liu, J. Org. Chem., 2021, 86,
14974-14982.
A highly
enantioselective and catalytic vinylation of aldehydes leads to allylic alcohols
that are then transformed to the allylic amines via Overman's [3,3]-sigmatropic
rearrangement of imidates. Oxidative cleavage of the allylic amines furnishes amino acids in good yields and excellent ee's. The scope and utility of this
method are demonstrated by the synthesis of challenging allylic amines and their
subsequent transformation to valuable nonproteinogenic amino acids, including
both D and L configured (1-adamantyl)glycine.
Y. K. Chen. A. E. Lurain, P. J. Walsh, J. Am. Chem. Soc., 2002, 124, 12225-12231.
Specific oxidation protocols have been developed for the cleavage of styrenes,
aliphatic olefins, and terminal aliphatic olefins to carbonyl compounds with
ruthenium trichloride as catalyst. Olefins that are not fully substituted are
converted to aldehydes rather than carboxylic acids.
D. Yang, C. Zhang, J. Org. Chem., 2001, 66, 4814-4818.