Categories: C=O Bond Formation > Synthesis of carboxylic acids >
Synthesis of carboxylic acids by oxidation of alcohols
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A metal-free, chemoselective oxidation of primary alcohols and aldehydes with
cheap 1-hydroxycyclohexyl phenyl ketone as oxidant to the corresponding
carboxylic acids features an easy to handle procedure, high isolated yields, and
good to excellent functional group tolerance even in the presence of vulnerable
secondary alcohols and tert-butanesulfinamides.
W.-Y. Tan, Y. Lu, J.-F. Zhao, W. Chen, H. Zhang, Org. Lett., 2021, 23,
6648-6653.
A simple and readily accessible cobalt pincer catalyst (NNNHtBuCoBr2)
mediates a facile oxidation of alcohols to carboxylate salts. This acceptorless dehydrogenation displays good
functional group tolerance.
D. R. Pradhan, S. Pattanaik, J. Kishore, C. Gunanathan,
Org. Lett., 2020, 22, 1852-1857.
Oxidation from alcohols to carboxylic acids are often conducted using at least a
stoichiometric amount of an expensive and toxic oxidant. An efficient and
practical sustainable oxidation technology of alcohols using pure O2
or even air as the oxidant in the presence of a catalytic amount each of Fe(NO3)3·9H2O/TEMPO/MCl
provides a series of carboxylic acids in high yields at room temperature.
X. Jiang, J. Zhang, S. Ma, J. Am. Chem. Soc., 2016,
138, 8344-8347.
A CrO3-catalyzed oxidation of primary alcohols to carboxylic acids
proceeds smoothly with only 1-2 mol % of CrO3 and 2.5 equivalents of
H5IO6 in wet MeCN to give the carboxylic acids in
excellent yield. No significant racemization is observed for alcohols with
adjacent chiral centers. Secondary alcohols are cleanly oxidized to ketones.
M. Zhao, J. Li, Z. Song, R. Desmond, D. M. Tschaen, E. J. J. Grabowski, P. J.
Reider, Tetrahedron Lett., 1998,
39, 5323-5326.
Various aromatic, aliphatic and conjugated alcohols were transformed into the
corresponding carboxylic acids and ketones in good yields with aq 70% t-BuOOH
in the presence of catalytic amounts of bismuth(III) oxide. This method
possesses does not involve cumbersome work-up, exhibits chemoselectivity and
proceeds under ambient conditions. The overall method is green.
P. Malik, D. Chakraborty, Synthesis, 2010, 3736-3740.
Pd/C along with NaBH4 in aqueous ethanol or methanol and either K2CO3
or KOH as base at room temperature under molecular oxygen or air is capable of
oxidizing alcohols to its desired carbonyl or carboxyl counterpart. Room
temperature reaction in aqueous system and recyclability of the catalyst make
the process safe and cheaper.
G. An, H. Ahn, K. A. De Castro, H. Rhee, Synthesis, 2010,
477-485.
A dehydrogenative reaction of primary alcohols in the presence of hydroxide and
the ruthenium complex [RuCl2(IPr)(p-cymene)] as catalyst
provides carboxylic acids. The use of toluene enables a simple product isolation
by precipitation and extraction. A range of benzylic and saturated aliphatic
alcohols containing halide and (thio)ether substituents can be converted, while
olefins and ester groups are not compatible.
C. Santilli, I. S. Makarov, P. Fristrup, R. Madsen, J. Org. Chem.,
2016, 81, 9931-9938.
Catalytic use of o-iodoxybenzoic acid (IBX) in the presence of Oxone as a
co-oxidant is demonstrated for the oxidation of primary and secondary alcohols.
In addition, the in situ oxidation
of 2-iodosobenzoic acid (IBA) and even commercially available 2-iodobenzoic acid
(2IBAcid) by Oxone to IBX allows the use of these less hazardous reagents, in
place of potentially explosive IBX, as catalytic oxidants.
A. P. Thottumkara, M. S. Bowsher, T. K. Vinod, Org. Lett., 2005, 7, 2933-2936.
A facile and quantitative preparation of carboxylic acids by a pyridinium
chlorochromate (PCC) catalyzed (2 mol%) oxidation of primary alcohols and
aldehydes using 2.2 equivalents and 1.1 equivalents of H5IO6, respectively, in
acetonitrile is described here.
M. Hunsen, Synthesis, 2005, 2487-2490.
The use of low loadings of a silver NHC catalysts enables a mild, selective
oxidation of alcohols to aldehydes or carboxylic acids in the presence of BnMe3NOH
or KOH under dry air in excellent yield. The catalytic system can also be used
for a one-pot synthesis of imines in excellent yield.
L. Han, P. Xing, B. Jiang, Org. Lett., 2014,
16, 3428-3431.
A facile and mild photooxidation of alcohols gives carboxylic acids and ketones
using easily handled 2-chloroanthraquinone as an organocatalyst under visible
light irradiation in an air atmosphere.
Y. Shimada, K. Hattori, N. Tada, T. Miura, A. Itoh, Synthesis, 2013, 45,
2684-2688.
Optimized selective aerobic oxidations in ionic liquids convert various
activated primary alcohols into their corresponding acids or aldehydes in good
to excellent yields. The newly developed catalytic systems could also be
recycled and reused for three runs without any significant loss of catalytic
activity.
N. Jiang, A. J. Ragauskas, J. Org. Chem.,
2007,
72, 7030-7033.
Catalytic amounts of TEMPO and NaOCl enable a chemoselective oxidation of
1,2-diols to in the presence of NaClO2 as terminal oxidant. The use
of a two-phase condition suppresses the concomitant oxidative cleavage. The
observed selectivity seems to be derived from the precise solubility control of
diols and hydroxy acids as well as the charge transfer complex TEMPO-ClO2,
which dissolves into the organic layer.
K. Furukawa, M. Shibuya, Y. Yamamoto, Org. Lett.,
2015,
17, 2282-2285.
A chiral bisoxazoline ligand/copper catalyst system mediates an asymmetric
oxidative desymmetrization of readily accessible 2-(hetero)aryl- and
alkyl-substituted glycerols with 1,3-dibromo-5,5-dimethylhydantoin and MeOH. The
present transformation provides straightforward access toward various glycerate
derivatives in good yields with high enantioselectivities.
K. Yamamoto, Y. Suganomata, T. Inoue, M. Kuriyama, Y. Demizu, O. Onomura, J. Org. Chem., 2022, 87,
6479-6491.
The use of a NaOtBu-O2 resulted in an efficient oxidative
cleavage of vic-1,2-diols to form carboxylic acids in high yields. The
present protocol is a green alternative to conventional transition metal based
methods. Large-scale production with nonchromatographic purification is also
possible.
S. M. Kim, D. W. Kim, J. W. Yang, Org. Lett., 2014,
16, 2876-2879.
A smooth, organocatalytic one-pot oxidative cleavage of terminal 1,2-diols to
one-carbon-unit-shorter carboxylic acids is catalyzed by 1-Me-AZADO in the
presence of a catalytica amount of NaOCl and NaClO2 under mild
conditions. A broad range of substrates including carbohydrates and N-protected
amino diols were converted without epimerization.
M. Shibuya, R. Doi, T. Shibuta, S.-i. Uesugi, Y. Iwabuchi, Org. Lett., 2012,
14, 5006-5009.
An aerobic photooxidative cleavage of vicinal diols yields carboxylic acids
using 2-chloroanthraquinone in the presence of photoirradiation with a
high-pressure mercury lamp. This is a metal-free reaction in which molecular
oxygen is used as the terminal oxidant.
Y. Matsusaki, T. Yamaguchi, N. Tada, T. Miura, A. Itoh, Synlett, 2012, 23,
2059-2062.
An atom-economical and environmentally friendly dehydrogenation of amino
alcohols to amino acid salts using just basic water, without the need of
pre-protection or added oxidant is catalyzed by a ruthenium pincer complex.
Water is the solvent, the source of the oxygen atom of the carboxylic acid group,
and the actual oxidant. Many important and useful natural and unnatural amino
acid salts can be produced in excellent yields.
P. Hu, Y. Ben-David, D. Milstein, J. Am. Chem. Soc., 2016,
138, 6143-6146.