IBX
2-Iodoxybenzoic acid (IBX), the impact-sensitive intermediate in the synthesis of the Dess-Martin periodinane, is available in a DMSO solution and is used as an oxidizing agent.
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.
K. Surendra, N. Srilakshmi Krishnaveni, M. Arjun Reddy, Y. V. D. Nageswar, K.
Rama Rao, J. Org. Chem., 2003,
68, 2058-2059.
Alcohols are oxidized to the corresponding carbonyl compounds with
iodoxybenzoic acid (IBX) or with Dess-Martin-Periodinane (DMP) in
[bmim]BF4 and [bmim]PF6 ionic liquids at room
temperature in excellent yields with high selectivity. These oxidations are faster in ionic liquids as compared to
conventional solvents. The byproduct
iodosobenzoic acid (IBA) and the ionic liquid are readily recovered.
J. S. Yadav, B. V. S. Reddy, A. K. Basak, A. V. Narsaiah, Tetrahedron,
2004,
60, 2131-2135.
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.
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.
A. P. Thottumkara, M. S. Bowsher, T. K. Vinod, Org. Lett.,
2005,
7, 2933-2936.
o-Iodoxybenzoic acid (IBX) was found to be highly effective in
oxidations adjacent to carbonyl and benzylic functionalities to form
either α,β-unsaturated carbonyl compounds or conjugated aromatic
carbonyl systems. Fine-tuning of the reaction conditions allowed
remarkably selective transformations within multifunctional substrates.
K. C. Nicolaou, T. Montagnon, P. S. Baran, Y.-L. Zhong, J. Am. Chem.
Soc., 2002,
124, 2245-2258.
K. C. Nicolaou, T. Montagnon, P. S. Baran, Y.-L. Zhong, J. Am. Chem.
Soc., 2002,
124, 2245-2258.
K. C. Nicolaou, T. Montagnon, P. S. Baran, Y.-L. Zhong, J. Am. Chem.
Soc., 2002,
124, 2245-2258.
The reduction of IBX to IBA in the presence of molecular iodine in DMSO
generates hypoiodous acid (IOH), which reacts with various olefins as well as
α,β-unsaturated ketones leading to their respective iodohydrins with anti
stereochemistry. The same redox chemistry in acetonitrile containing TFA
produces iodonium ions for facile iodination of aromatic compounds.
J. N. Moorthy, K. Senapati, S. Kumar, J. Org. Chem., 2009,
74, 6287-6290.
Utilizing the full potential of IBX, a mild, selective, and facile method
enables a direct conversion of olefins into the corresponding α-bromo ketones in
the presence of 1.1 equivalents each of o-iodoxybenzoic acid and
tetraethylammonium bromide.
S. S. Deshmukh, K. H. Chaudhari, K. G. Akamanchi, Synlett, 2011,
81-83.
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.
1,3-Diols undergo smooth oxidative cleavage of the C-C bond in the presence of
2-iodoxybenzoic acid (IBX) affording 1,2-diketones in excellent yields under
mild conditions.
J. S. Yadav, S. K. Biswas, R. Srinivas,
Synthesis, 2006, 4237-4241.
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 clean and efficient method for the oxidative transformations of primary
carboxamides to one-carbon dehomologated nitriles using the combination of
o-iodoxybenzoic acid and tetraethylammonium bromide exhibits a broad scope and
is expected to be of great utility in organic synthesis.
D. S. Bhalarao, U. S. Mahajan, K. H. Chaudhari, K. G. Akamanchi, J. Org. Chem., 2007,
72, 662-665.
An efficient and mild oxidative desulfurization procedure using o-iodoxybenzoic
acid enables the synthesis of carbodiimides starting from easily available
1,3-disubstituted thioureas.
P. S. Chaudhari, P. S. Dangate, K. G. Akamanchi, Synlett, 2010,
3065-3067.
A novel and facile transformation of N,N-disubstituted glycylamides into
corresponding cyanamides using pentavalent iodine reagents and
tetraethylammonium bromide offers advantages such as use of non toxic reagents,
shorter reaction times and good yields.
K. H. Chaudhari, U. S. Mahajan, D. S. Bhalerao, K. G. Akamanchi, Synlett,
2007, 2815-2818.
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.
The reaction of aldehydes, amines, and TMSCN in the presence of 2-iodoxybenzoic
acid (IBX) and tetrabutylammonium bromide (TBAB) afforded α-iminonitriles in
good to excellent yields under mild conditions. The presence of TBAB is
essential for this transformation.
P. Fontaine, A. Chiaroni, G. Masson, J. Zhu, Org. Lett., 2008,
10, 1509-1512.
K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, Angew. Chem. Int. Ed., 2003,
42, 4077-4082.
K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, Angew. Chem. Int. Ed., 2003,
42, 4077-4082.
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.
The α-hydroxylation of α-alkynyl carbonyl compounds using IBX (o-iodoxybenzoic
acid) gave various α-hydroxyketones without dehydrogenation products
under mildly acidic conditions.
S. F. Kirsch, J. Org. Chem., 2005,
70, 10210-10212.
S. F. Kirsch, J. Org. Chem., 2005,
70, 10210-10212.
Hantzsch 1,4-dihydropyridines undergo smooth aromatization catalyzed by
iodoxybenzoic acid (IBX) to afford the corresponding pyridine
derivatives in high yields. All the reactions were carried out in DMSO
solvent at 80-85 °C for a period of two to four hours to complete
conversion of the substrates.
J. S. Yadav, B. V. S. Reddy, A. K. Basak, G. Baishya, A. V. Narsaiah,
Synthesis, 2006, 451-454.
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.
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.
