Categories: C=O Bond Formation > Synthesis of ketones >
Synthesis of ketones by hydrolysis or deprotection
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 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.
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.
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.
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.
