Categories: C=O Bond Formation > Synthesis of ketones >
Synthesis of ketones by oxidation of alcohols
Name Reactions
Recent Literature
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.
The combination of TEMPO and CAN can be used for the aerobic oxidation of
benzylic and allylic alcohols into their corresponding carbonyl compounds.
However, steric hindrance has been observed to impede the reaction with some
substituted allylic systems. The present method is superior to others
currently available due to its relatively short reaction times and excellent
yields.
S. S. Kim, H. C. Jung, Synthesis, 2003, 2135-2137.
A rapid oxidation of primary and secondary alcohols using catalytic amounts of
TEMPO and Yb(OTf)3 in combination with a stoichiometric amount of
iodosylbenzene afforded carbonyl compounds in excellent yields without
over-oxidation. Oxidation of primary alcohols in the presence of secondary
alcohols proceeded with good selectivity.
J.-M. Vatèle, Synlett, 2006,
2055-2058.
A novel, metal-free oxidation system for the catalytic synthesis of aldehydes
and ketones using TEMPO and a quarternary ammonium salt as catalysts and Oxone
as oxidant proved especially successful for the synthesis of ketones. The mild
conditions tolerate even sensitive silyl protective groups which can otherwise
be cleaved in the presence of Oxone.
C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000, 2,
1173-1175.
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 new, green, mild and inexpensive system, I2-KI-K2CO3-H2O,
selectively oxidized alcohols to aldehydes and ketones under anaerobic condition
in water at 90 °C with excellent yields.
P. Gogoi, D. Konwar, Org. Biomol. Chem., 2005, 3, 3473-3475.
A simple, efficient, and high-yield procedure for the oxidative conversion of
alcohols to various types of esters and ketones was successfully carried out
with molecular iodine as the oxidant and potassium carbonate.
N. Mori, H. Togo, Tetrahedron, 2005,
61, 5915-5925.
A chemoselective and efficient procedure allows the conversion of benzylic
and allylic alcohols into the corresponding carbonyl compounds with sodium
nitrate as oxidant in the presence of 3-methylimidazolinium hydrogensulfate.
A. R. Hajipour, F. Rafiee, A. E. Ruoho, Synlett, 2007,
1118-1119.
Keggin-type heteropoly acids revealed high catalytic activity for swift and
selective oxidation of various hydroxy functionalities to the corresponding
carbonyl groups using ferric nitrate as an oxidant under mild and solvent-free
conditions.
H. Firouzabadi, N. Iranpoor, K. Amani, Synthesis, 2003, 408-412.
A highly efficient and mild procedure for the oxidation of different types of
alcohols uses TEMPO as catalyst, iodobenzene dichloride as stoichiometric
oxidant, and pyridine as base. Oxidation of 1,2-diols gives α-hydroxy ketones or
α-diketones depending on the amount of oxidant used. High yielding procedures
for the preparation of iodoarene dichlorides have been developed.
X.-F. Zhao, C. Zhang, Synthesis, 2007,
551-557.
The oxidation of primary and secondary alcohols by sodium percarbonate in the presence of catalytic
amounts of both molybdenyl acetylacetonate and Adogen 464 gave fair to high yields
of the corresponding carbonyl compounds.
S. Maignien, S. Aït-Mohand, J. Muzart, Synlett, 1996, 439-440.
A chemoselective oxidation of secondary alcohols with IBX/n-Bu4NBr
in CH2Cl2-H2O gave ketones in good yields and
allowed the oxidation of secondary hydroxyl group even in the presence of
primary hydroxyl groups.
C. Kuhakarn, K. Kittigowittana, M. Pohmakotr, V. Reutrakul, Tetrahedron, 2005,
61, 8995-9000.
Permanganate supported on active manganese dioxide can be used effectively
for the oxidation of arenes, alcohols and sulfides under heterogeneous or
solvent-free conditions.
A. Shaabania, P. Mirzaeia, S. Naderia, D. G. Leeb, Tetrahedron, 2004, 60, 11415-11420.
Benzyl alcohols and benzyl TBDMS ethers were
efficiently oxidized to the corresponding carbonyl compounds in high yield with
periodic acid catalyzed by CrO3 at low temperature (-78 °C). The oxidation
procedure was highly functional group tolerant and very selective for the TBDMS
group over the TBDPS group.
S. Zhang, L. Xu, M. L. Trudell, Synthesis, 2005,
1757-1760.
Pd/C in aqueous alcohol with molecular oxygen, sodium borohydride,
and potassium carbonate efficiently oxidized benzylic and allylic alcohols.
Sodium borohydride allows a remarkable reactivation of active sites of the Pd
surface.
G. An, M. Lim, K.-S. Chun, H. Rhee, Synlett, 2007, 95-98.
A new, highly recoverable palladium-based catalyst for the aerobic oxidation
of alcohols combines an organic ligand and mesoporous channels that led to
enhanced activity, prevention of agglomeration and the generation of a
durable catalyst.
B. Karimi, S. Abedi, J. H. Clark, V. Budarin, Angew. Chem. Int. Ed., 2006, 45, 4776-4779.
A robust and effective Pd catalyst for the aerobic oxidation of various alcohols
has been discovered. Using a slightly higher concentration of acetic acid as
additive and extending the reaction times, the oxidation can be carried out
under ambient atmosphere of air.
D. R. Jensen, M. J. Schultz, J. A. Mueller, M. S. Sigman, Angew. Chem.
Int. Ed.,
2003, 42, 3810-3813.
[dibmim][BF4] can be used for the oxidation
of alcohols to carbonyl compounds. This oxidizing agent offers a high
degree of selectivity for the oxidation of primary alcohols to carbonyl
compounds without oxidation to carboxylic acids in ionic liquids. [dibmim][BF4]
can be reused after oxidation with peracetic acid.
W. Qian, E. Jin, W. Bao, Y. Zhang, Angew. Chem. Int. Ed., 2005,
44, 952-955.
A practical and environmentally friendly method for the
oxidative rearrangement of five- and six-membered cyclic tertiary allylic
alcohols to α,β-unsaturated β-disubstituted ketones by IBX in DMSO
is described. Several conventional protecting groups (e.g., Ac, MOM, and TBDPS)
are tolerated.
M. Shibuya, S. Ito, M. Takahashi, Y. Iwabuchi, Org. Lett., 2004, 6, 4303-4306.
An efficient oxidant-free oxidation for a wide range of alcohols was
achieved by a recyclable ruthenium catalyst, which was prepared from readily
available reagents through nanoparticle generation and gelation.
W.-H. Kim, I. S. Park, J. Park, Org. Lett.,
2006, 8, 2543-2545.
Adsorbed [RuCl2(p-cymene)]2
on activated carbon is an efficient, environmentally attractive and highly
selective catalyst for use in aerobic oxidations, hydrolytic oxidations and
dehydrations. The heterogeneous catalyst was recovered quantitatively by simple
filtration and could be reused with minimal loss of activity.
E. Choi, C. Lee, Y. Na, S. Chang, Org. Lett., 2002, 4,
2369-2371.
A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and
secondary alcohols in ionic liquid [bmim][PF6] gave the
corresponding aldehydes and ketones with no trace of overoxidation to carboxylic
acids. The product can be isolated by a simple extraction with organic solvent,
and the ionic liquid can be recycled or reused.
I. A. Ansari, R. Gree, Org. Lett., 2002, 4, 1507-1509.
Oxidation of alcohols to aldehydes and ketones were performed under
atmospheric oxygen with a catalytic amount of V2O5 in
toluene at 100°C. Secondary alcohols can be chemoselectively converted into
ketones in the presence of primary hydroxy groups.
S. Velusamy, T. Punniyamurthy, Org. Lett., 2004, 6,
217-219.
Trihaloacetic acids can been converted to trichloromethyl and tribromomethyl ketones in good
yield by a catalyzed reaction with aldehydes followed by oxidation. A coupling of organozinc intermediates with trichloroacetyl chloride
gives trichloromethyl ketones.
E. J. Corey, J. O. Link, Y. Shao, Tetrahedron Lett., 1992,
33, 3435-3438.
