Categories: C=O Bond Formation > Synthesis of ketones
Synthesis of α-hydroxy ketones and aldehydes
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Various terminal olefinic compounds are directly
converted into the corresponding α-hydroxy ketones in good yields by potassium
permanganate oxidation. The reaction is highly chemoselective in the
presence of differently protected hydroxy groups.
C. Bonini, L. Chiummiento, M. Funicello, P. Lupattelli, M. Pullez, Eur. J. Org. Chem., 2006,
80-83.
A direct, mild ketohydroxylation of various 1-aryl-1-alkenes with H2O2,
catalyzed by the inexpensive 12-tungstophosphoric acid/cetylpyridinium
chloride system, gave acyloins in good yields and high regioselectivies.
Y. Zhang, Z. Shen, J. Tang, Y. Zhang, L. Kong, Y. Zhang, Org. Biomol. Chem., 2006, 4, 1478-1482.
A palladium-catalyzed, environmentally friendly dioxygenation reaction of simple
alkenes enables a rapid assembly of valuable α-hydroxy ketones with high atom
economy.
J. Huang, J. Li, J. Zheng, W. Wu, W. Hu, L. Ouyang, H. Jiang, Org. Lett.,
2017, 19, 3354-3357.
I2-catalyzed oxo-acyloxylation of alkenes and enol ethers with
carboxylic acids provides α-acyloxyketones and esters in high yields. This
unprecedented regioselective oxidative process employs TBHP and Et3N
in stoichiometric amounts under metal-free conditions in DMSO as solvent.
α-Acyloxyketones can be converted in situ to monoprotected diol derivatives in
excellent yields upon treatment with BH3·SMe2.
R. N. Reddi, P. K. Prasad, A. Sudalai, Org. Lett.,
2014,
16, 5674-5677.
A practical and environmentally friendly oxidation of aryl olefins to
arylethanone derivatives by using a Cu(I) catalyst and tert-butyl
hydroperoxide (TBHP) provides 2-tert-butoxy-1-arylethanones in good
yields under mild conditions with high selectivity. In this method, TBHP acts
not only as an oxidant but also as the tert-butoxy and carbonyl oxygen
sources.
J. Zhang, D. Xiao, H. Tan, W. Liu, J. Org. Chem., 2020, 85,
3929-3935.
Cobalt bis(acetylacetonate) mediates hydrogen atom transfer to a broad range of
functionalized alkenes. In situ oxidation of the resulting alkylradical
intermediates, followed by hydrolysis, provides expedient access to ketones and
esters. This method is compatible with a number of functional groups and
provides a mild and practical alternative to the Tamao-Fleming oxidation of
vinylsilanes and the Arndt-Eistert homologation.
X. Ma, S. B. Herzon, J. Org. Chem.,
2016, 81, 8673-8695.
Phenyliodonium diacetate mediates a synthesis of α-oxygenated ketones from
styrenes in the presence of molecular oxygen and N-hydroxyphthalimide or
N-hydroxybenzotriazole under metal-free conditions. The present method is
applicable for wide range of styrenes with various functional groups.
S. Samanta, R. R. Donthiri, C. Ravi, S. Adimurthy, J. Org. Chem.,
2016,
81, 3457-3463.
The combination of electrochemical
synthesis and aerobic oxidation enables a transition-metal-free dioxygenation of alkenes to
provide α-oxygenated
ketones in an eco-friendly fashion. A wide
range of alkenes and N-hydroxyimides provided
α-oxygenated ketones in good yields.
C. Dai, Y. Shen, Y. Wei, P. Liu, P. Sun, J. Org. Chem., 2021, 86,
13711-13719.
The use of PhI(OAc)2 enables an efficient access to α,α′-diacetoxy
ketones has from ethynylcarbinols. Glycerol derivatives can be easily
synthesized in good yields via a one-pot reaction. A plausible mechanism is
proposed.
Q.-R. Liu, C.-X. Pan, X.-P. Ma, D.-L. Mo, G.-F. Su, J. Org. Chem.,
2015,
80, 6496-6501.
A highly enantioselective method for catalytic reductive coupling of alkynes
and aldehydes afforded allylic alcohols with complete E/Z selectivity,
generally >95:5 regioselectivity, and in up to 96% ee. In conjunction with
ozonolysis, this process allows the enantioselective synthesis of α-hydroxy
ketones.
K. M. Miller, W.-S. Huang, T. F. Jamison, J. Am. Chem. Soc., 2003, 125, 3442-3443.
IBX has been utilized for the oxidation of various epoxides and aziridines as
their β-cyclodextrin complexes in water to afford α-hydroxyketones and α-aminoketones
in good yields, respectively.
K. Surendra, N. S. Krishnaveni, M. A. Reddy, Y. V. D. Nageswar, K. R. Rao, J.
Org. Chem., 2003, 68, 9119-9121.
A mild and efficient oxidation of alcohols with o-iodoxybenzoic acid
(IBX) is catalyzed by β-cyclodextrin in a water/acetone mixture (86:14).
Various alcohols were oxidized at room temperature in
excellent yields.
K. Surendra, N. Srilakshmi Krishnaveni, M. Arjun Reddy, Y. V. D. Nageswar, K.
Rama Rao, J. Org. Chem., 2003,
68, 2058-2059.
A two-step sequence of asymmetric dihydroxylation and regioselective
monooxidation gave enantiopure α-hydroxy ketones (acyloins). The
combination of RuCl3/Oxone/NaHCO3 was used in the
first catalytic regioselective oxidation of vic-diols to α-ketols.
B. Plietker, Org. Lett., 2004, 6, 289-291.
A catalyst comprising of Ph3PAuCl and AgSbF6 efficiently
hydrolyzes terminal alkyne groups of propargyl acetates in the absence of acid
promoters at ambient temperature within a short time. Effective regioselective
hydration is facilitated by the neighboring carbonyl group. Synthesis of
actinopolymorphol B is achieved involving hydration of the propargyl acetate as
the key step.
N. Ghosh, S. Nayak, A. K. Sahoo, J. Org. Chem., 2011,
76, 500-511.
Transformation of epoxides to β-alkoxy alcohols, acetonides, and α-alkoxy
ketones is achieved by using molybdenum(VI) dichloride dioxide (MoO2Cl2)
as a catalyst. Alcohol, aldehyde, oxime, tosyl, and tert-butyldimethylsilyl
functional groups are tolerated during the methanolysis and acetonidation of the
functionalized epoxides.
K. Jeyakumar, D. K. Chand, Synthesis, 2008,
807-819.
Enol esters can be epoxidized with high enantioselectivities using a
fructose-derived chiral ketone as catalyst and Oxone as oxidant. A subsequent
acid-catalyzed rearrangement can proceed through two distinct pathways, one with
retention of configuration and the other with inversion. Whereas a strong acid
favors retention of configuration, a weak acid favors inversion of
configuration.
Y. Zhu, L. Shu, Y. Tu, Y. Shi, J. Org. Chem., 2001,
66, 1818-1826.
Grubbs' 2nd generation metathesis catalyst can be used in tandem olefin
metathesis/oxidation protocols. These ruthenium-catalyzed processes provide
access to cis-diols or α-hydroxy ketones from simple olefinic starting
materials.
A. A. Scholte, M. H. An, M. L. Snapper, Org. Lett.,
2006, 8, 4759-4762.