Categories: C=O Bond Formation > Synthesis of ketones >
Synthesis of ketones by hydrolysis, deprotection, or oxidation
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Name Reactions
Protecting Groups
1,3-Dithianes, 1,3-Dithiolanes
Recent Literature
Oximes of various aldehydes and ketones can be converted to the
corresponding carbonyl compounds at room temperature in excellent yields
with 2-iodylbenzoic acid in water in the presence of β-cyclodextrin.
N. S. Krishnaveni, K. Surendra, Y. V. D. Nageswar, K. R. Rao, Synthesis, 2003, 1968-1969.
Carbonyl compounds were obtained in very good yields after treatment of oximes
with 2 molar equivalent of CuCl2 • 2 H2O at reflux in
acetonitrile and water (4:1). In addition, cupric salt was readily recovered in
an almost quantitative yield via the complete precipitation of Cu(OH)2
• 2 H2O.
N. Quan, X.-X. Shi, L.-D. Nie, J. Dong, R.-H. Zhu, Synlett, 2011,
1028-1032.
N-bromosaccharin is an efficient reagent for the oxidative cleavage of
oximes to the corresponding aldehydes and ketones under microwave irradiation in
a domestic microwave oven. This procedure features short reaction times, high
chemoselectivity (no over-oxidation), easy work-up and high yields.
A. Khazaei, A. A. Manesh, Synthesis,
2004,
1739-1740.
A BODIPY dye catalyzes an efficient and mild rearrangement of oximes to
amides or hydrolysis to ketones/aldehydes under visible light irradiation in the
presence of air as an oxidant. The triplet excited state of BODIPY played a
significant role in the catalytic process.
X. Peng, Y. liu, Q. Shen, D. Chen, X. Chen, X. Fu, J. Wang, X. Zhang, H.
Jiang, J. Li, J. Org. Chem., 2022, 87,
11952-11967.
A simple, mild and efficient procedure cleaves a wide range of ketoximes and
aldoximes to the corresponding carbonyl compounds in an aqueous medium using
catalytic amounts of potassium bromide and ammonium heptamolybdate tetrahydrate
in combination with hydrogen peroxide.
N. C. Ganguly, S. K. Barik, Synthesis, 2008,
425-428.
I2 catalyzes the deprotection of oximes and imines to the
corresponding carbonyl compounds under neutral conditions in a water/surfactant
system at 25-40°C in high yields.
P. Gogoi, P. Hazarika, D. Konwar, J. Org. Chem., 2005, 70,
1934-1936.
A combination of PhI(OAc)2 and BF3·Et2O
promoted the Beckmann rearrangement of ketoximes to provide amides. The Beckmann
rearrangement is preceded by acetylation of the hydroxy group of the ketoxime in
situ, accelerating the Beckmann rearrangement. The reaction of ketoximes with
Koser's reagent in the presence of THF provides ketones in high yields at room
temperature.
T. Maegawa, R. Oishi, A. Maekawa, K. Segi, H. Hamamoto, A. Nakamura, Y. Miki, Synthesis, 2022, 54,
4095-4103.
Various aliphatic and aromatic oximes were converted to their corresponding
aldehydes and ketones in good to excellent yields in the presence of
2-nitro-4,5-dichloropyridazin-3(2H)-one under microwave irradiation. It
is noteworthy that the reaction is conducted under neutral, mild, and
eco-friendly condition.
B. R. Kim, H.-G. Lee, E. J. Kim, S.-G. Lee, Y.-J. Yoon, J. Org. Chem., 2010,
75, 484-486.
A rapid and efficient oxidative deamination of various α-aminophosphonates
allows the synthesis of α-ketophosphonates using ZnCr2O7 •
3 H2O under solvent-free conditions at room temperature. This method
is also applicable to the rapid and highly selective oxidation of various amines
to aldehydes and ketones in very good yields.
S. Sobhani, M. F. Maleki, Synlett, 2010, 382-386.
α-Keto esters can be prepared via Mannich addition of ethyl diazoacetate to
imines followed by oxidation of the diazo group with Oxone. Implementation of a
recently developed dynamic kinetic resolution of β-substituted-α-keto esters via
Ru(II)-catalyzed asymmetric transfer hydrogenation provides enantioenriched
anti-α-hydroxy-β-amino acid derivatives in high diastereo- and
enantioselectivity.
C. G. Goodman, D. T. Do, J. S. Johnson, Org. Lett., 2013,
15, 2446-2449.
A transition-metal-free coupling of aldehydes and ketones with geminal bis(boron)
building blocks provides homologated carbonyl compounds upon oxidation.
Aldehydes with an enolizable stereogenic center undergo this reaction with
complete retention of stereochemistry.
T. C. Stephens, G. Pattison, Org. Lett.,
2017, 19, 3498-3501.
An efficient and convenient procedure has been developed for the hydrolysis
of thioacetals/thioketals to the corresponding carbonyl compounds in
excellent yields with o-iodoxybenzoic acid (IBX) in presence of
β-cyclodextrin (β-CD) in water under neutral conditions at room temperature.
N. S. Krishnaveni, K. Surendra, Y. V. D. Nageswar, K. R. Rao, Synthesis, 2003, 2295-2297.
A number of new reactions of IBX with heteroatom-containing substrates were
discovered and their utility was demonstrated. IBX was used for the generation
of imines from secondary amines in notably high yields, for the oxidative
aromatization of nitrogen heterocycles and for the cleavage of dithianes.
K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, Angew. Chem. Int. Ed., 2003,
42, 4077-4082.
In the presence of hydrogen peroxide and trimethylsilyl chloride, thiocarbonyls
desulfurize to the corresponding carbonyls in short reaction times with no side
reactions and excellent selectivity. This process is a safe, operationally
simple, and environmentally benign alternative for the desulfurization of
thiocarbonyls.
K. Bahrami, M. M. Khodaei, M. Tajik, Synthesis, 2010,
4282-4286.
Perchloric acid adsorbed on silica gel is an extremely efficient, inexpensive,
and reusable catalyst for the protection of aldehydes and ketones and the
subsequent deprotection. Acetalization was mostly carried out under solvent-free
conditions with trialkyl orthoformates, but weakly electrophilic carbonyl
compounds and substrates that can coordinate with the catalyst, required the
corresponding alcohol as solvent.
R. Kumar, D. Kumar, A. K. Chakraborti, Synthesis, 2007, 299-303.
Er(OTf)3 is a very gentle Lewis acid catalyst in the
chemoselective cleavage of alkyl and cyclic acetals and ketals at room
temperature in wet nitromethane.
R. Dalpozzo, A. De Nino, L. Maiuolo, M. Nardi, A. Procopio, A. Tagarelli, Synthesis, 2004, 496-498.
Exo-3-furanylidenes and 3-pyranylidenes products having cis-2,5
and cis-2,6 substitution were synthesized from terminally substituted
alkynyl alcohols with various aldehydes via Prins-type cyclization and trapping
of the resulting vinyl cations as vinyl triflates in good yields. Vinyl
triflates underwent a subsequent stereoselective hydrolysis to give the
corresponding 3-acyl-substituted products.
S. N. Chavre, H. Choo, J. K. Lee, A. N. Pae, Y. Kim, Y. S. Cho, J. Org. Chem., 2008,
73, 7467-7471.
Silylated cyanohydrins of iodo-substituted aryl, heteroaryl, or cycloalkenyl
ketones undergo an I/Mg-exchange using i-PrMgCl·LiCl. After
subsequent reactions with electrophiles, a facile deprotection
produces polyfunctional ketones in good overall yiels. An extension to
aromatic iodoaldehydes is described.
C.-Y. Liu, H. Ren, P. Knochel, Org. Lett.,
2006, 8, 617-629.
α,α-Disubstituted acetamides undergo oxidative mild, efficient, and general
dehomologation to give one-carbon-shorter ketones when reacted with the
hypervalent iodine reagent o-iodoxybenzoic acid (IBX) in combination with
tetraethylammonium bromide (TEAB).
E. V. Bellale, D. S. Bhalarao, K. H. Chaudhari, K. G. Akamanchi, J. Org. Chem., 2008,
73, 9473-9475.
The use of alkali metal hydrides as reagents enables a mild, efficient protocol
for the aerobic oxidative cleavage of C-C bonds in aldehydes. The method is
applicable to a broad substrate range.
S. A. Shipilovskikh, A. E. Rubtsov, A. V. Malkov, Org. Lett.,
2017, 19, 6760-6762.
The visible-light mediated oxidative C-C bond cleavage of aldehydes has been
achieved in good yields at ambient temperature and open to air using Ru(bpy)3Cl2
as the photoredox catalyst.
H. Sun, C. Yang, F. Gao, Z. Li, W. Xia, Org. Lett., 2013,
15, 624-627.
An electrochemical oxidative decarboxylation of wide range of disubstituted
malonic acids leads to dimethoxy ketals in very good yields in the presence of
NH3. Treatment of the crude reaction mixture after electrolysis with
1 M aq HCl enables the synthesis of ketones in a single vessel operation.
X. Ma, Y. Luo, S. Dochain, C. Mathot, I. E. Marko, Org. Lett.,
2015,
17, 4690-4693.
A transition-metal-free oxidative C-C bond cleavage process for a broad range of
ester and dicarbonyl compounds involves carbanion addition to nitrosobenzene and
proceeds via fragmentation of a previously unobserved oxazetidin-4-one
heterocycle.
J. N. Payette, H. Yamamoto, J. Am. Chem. Soc., 2008,
130, 12276-12278.
An efficient and mild fluorination of vinyl azides enables the synthesis of
α-fluoroketones via a single-electron transfer (SET) and a subsequent fluorine
atom transfer.
S.-W. Wu, F. Liu, Org. Lett.,
2016, 18, 3642-3645.
A reaction between terminal alkynes and sulfonamides under ambient
air using PIDA (diacetoxy iodobenzene) provides α-sulfonylamino ketones. This
metal-free reaction offers a broad substrate scope, excellent regioselectivity,
easily accessible reactants, and mild reaction conditions and is operationally
simple.
S. Mahato, S. Santra, G. V. Zyryanov, A. Majee, J. Org. Chem., 2019, 84,
3176-3183.
N-Sulfonyl-1,2,3-triazoles react with water in the presence of a rhodium
catalyst to produce α-amino ketones in high yield. This transformation formally
achieves 1,2-aminohydroxylation of terminal alkynes in a regioselective fashion
in combination with a copper(I)-catalyzed 1,3-dipolar cycloaddition with N-sulfonyl
azides.
T. Miura, T. Biyajima, T. Fujii, M. Murakami, J. Am. Chem. Soc., 2012,
134, 194-196.
A practical Cu-catalyzed C(sp3)-C(sp2) cross-coupling of alkylsilyl peroxides with arylboronic acids
provides alkyl-substituted aromatic rings
smoothly at room temperature. The reductive cleavage of the O-O bond and the desired
cross-coupling reactions are promoted by simple Cu-based catalysts and do not
require activation by visible light.
S. Sakurai, S. Tsuzuki, R. Sakamoto, K. Maruoka, J. Org. Chem., 2020, 85,
3973-3980.