Iodosobenzene Diacetate, Phenyliodonium Diacetate, PIDA
Recent Literature
LiBr is an efficient catalyst for the dihydroxylation of alkenes to afford
either syn or anti diols with excellent diastereoselectivity
depending upon the use of NaIO4 or PhI(OAc)2 as the
oxidants.
L. Emmanuvel, T. M. A. Shaikh, A. Sudalai, Org. Lett.,
2005,
7, 5071-5074.
Copper(I) or -(II) salts with weakly coordinating anions catalyze a mild
diacetoxylation of olefins efficiently in the presence of PhI(OAc)2
as the oxidant. The reaction is effective for aryl, aryl alkyl, as well as
aliphatic terminal and olefins forming the corresponding vicinal diacetoxy
compounds in good yields. Internal olefins lead to syn/anti mixtures of up to
5.2.
J. Seayad, A. M. Seayad, C. L. L. Chai, Org. Lett., 2010,
12, 1412-1415.
The use of PhI(OAc)2 in dichloromethane enables a clean oxidative
cleavage of 1,2-diols to aldehydes. In the presence of OsO4 as
catalyst, NMO and 2,6-lutidine, olefinic bonds can be cleaved in acetone/water
to yield the corresponding carbonyl compounds.
K. C. Nicolaou, V. A. Adsool, C. R. H. Hale, Org. Lett., 2010,
12, 1552-1555.
K. C. Nicolaou, V. A. Adsool, C. R. H. Hale, Org. Lett., 2010,
12, 1552-1555.
A hypervalent iodine reagent, (diacetoxyiodo)benzene, and catalytic amount of
sodium azide in acetonitrile enable an oxidative decarboxylation of 2-aryl
carboxylic acids into the corresponding aldehydes, ketones, and nitriles in good
yields at room temperature. The advantages of this protocol are short reaction
times and mild reaction conditions.
V. N. Telvekar, K. A. Sasane, Synlett, 2010,
2778-2779.
Pd-catalyzed selective oxidation of Boc-protected N-methylamines with
IOAc as the oxidant involves a Boc-directed C-H activation process.
D.-H. Wang, X.-S. Hao, D.-F. Wu, J.-Q. Yu, Org. Lett.,
2006,
8, 3387-3390.
Copper(II) trifluoromethanesulfonate catalyzed a mild amidation of cyclic ethers
with iminoiodanes with good yields and selectivity. A subsequent reductive
ring-opening of the tosylamidated products gives α,ϖ-amino alcohols.
L. He, J. Yu, J. Zhang, X.-Q. Yu, Org. Lett., 2007,
9, 2277-2280.
A new palladium-catalyzed method allows the oxygenation of unactivated sp3
C-H bonds of a wide variety of alkane substrates containing readily
available oxime and/or pyridine directing groups with extremely high levels
of chemo-, regio-, and in some cases diastereoselectivity.
L. V. Desai, K. L . Hull, M. S. Sanford, J. Am. Chem. Soc.,
2004,
126, 9542-9543.
A palladium-catalyzed intramolecular diamination reaction yields cyclic
ureas as direct products of an oxidative alkene transformation in the
presence of iodosobenzene diacetate as terminal oxidant.
J. Streuff, C. H. Hövelmann, M. Nieger, K. Muniz, J. Am. Chem. Soc.,
2005,
127, 14586-14587.
An intermolecular Pd-catalyzed aminoacetoxylation of alkenes with phthalimide
as the nitrogen source and PhI(OAc)2 as the stoichiometric oxidant
and source of acetate achieves a highly regio- and diastereoselective oxidative
1,2-difunctionalization of alkenes. The mechanism is discussed.
G. Liu, S. S. Stahl, J. Am. Chem. Soc.,
2006,
128, 7179-7181.
A catalytic Mitsunobu reaction system is described in which the azo reagent
is used as an organocatalyst and iodosobenzene diacetate is used as the
stoichiometric oxidant. Yields obtained in the catalytic reactions of carboxylic
acids and alcohols were slightly lower than those obtained from corresponding
stoichiometric reactions.
T. Y. S. But, P. H. Toy, J. Am. Chem. Soc., 2006,
128, 9636-9637.
A gold(I) compound, supported by 4,4',4' '-tri-tert-butyl-2,2':6',2' '-terpyridine
(tBu3tpy) as the ligand, efficiently catalyzes olefin
aziridination with the use of the commercially available oxidant PhI(OAc)2
and sulfonamides.
Z. Li, X. Ding, C. He, J. Org. Chem., 2006,
71, 5876-5880.
Various 2-arylbenzimidazoles were synthesized from phenylenediamines and
aldehydes via a one-step process using hypervalent iodine as oxidant. This
method features mild conditions, short reaction times, high yields, and a simple
procedure.
L-H. Du, Y.-G. Wang, Synthesis, 2007,
675-678.
2-Imidazolines were easily prepared in good yields from the reaction of
aldehydes and ethylenediamine with iodine in the presence of potassium carbonate.
The 2-imidazolines were smoothly oxidized to the corresponding imidazoles in
good yields using (diacetoxyiodo)benzene at room temperature.
M. Ishihara, H. Togo, Synlett,
2006, 227-230.
Iodobenzene diacetate efficiently oxidizes aldoximes to nitrile oxides in MeOH
containing a catalytic amount of TFA. Nitrile oxides may be trapped in situ with
olefins in a bimolecular or an intramolecular mode. Tandem oxidative
dearomatization of phenols/intramolecular nitrile oxide cycloaddition sequences
lead to useful synthetic intermediates.
B. A. Mendelsohn, S. Lee, S. Kim, F. Tayssier, V. S. Aulakh, M. A. Ciufolini, Org. Lett., 2009,
11, 1539-1542.
Various substituted enamine derivatives can be conveniently converted to the
corresponding 2H-azirines mediated by phenyliodine (III) diacetate (PIDA).
The formed 2-aryl-2H-azirines allow the synthesis of
indole-3-carbonitriles or isoxazoles via thermal rearrangements.
X. Li, Y. Du, Z. Liang, X. Li, Y. Pan, K. Zhao, Org. Lett., 2009,
11, 2643-2646.
A Pd(II)-catalyzed C-H bond amination reaction operates under extremely mild
conditions and produces carbazole products in good to excellent yields.
Carbazoles possessing complex molecular architecture can also be formed using
this reaction, highlighting its potential in natural product synthesis
applications.
J. A. Jordan-Hore, C. C. C. Johansson, M. Gulias, E. M. Beck, M. J. Gaunt, J. Am. Chem. Soc., 2008,
130, 16184-16186.
A new Pd-catalyzed oxidation reaction for the stereospecific conversion of
enynes into cyclopropyl ketones proceeds with net inversion of geometry with
respect to the starting olefin. This result is consistent with a mechanism in
which the key cyclopropane-forming step involves nucleophilic attack of a
tethered olefin onto the PdIV-C bond.
L. L. Welbes, T. W. Lyons, K. A. Cychosz, M. S. Sanford, J. Am. Chem. Soc., 2007,
129, 5836-5837.
Acetyl hypoiodite (CH3CO2I) is readily generated in situ
by oxidation of molecular iodine by (diacetoxyiodo)benzene (DAIB) and can be
utilized for the synthesis of 1,2-iodo-cofunctionalized derivatives of alkenes.
Conversion of both atoms of molecular iodine to I+ results in 100%
iodine atom economy for the reported iodo-cofunctionalization of alkenes.
H. Gottam, T. K. Vinod, J. Org. Chem., 2011,
76, 974-977.
Treatment of terminal alkynes with (diacetoxyiodo)benzene, potassium iodide, and
copper(I) iodide afforded 1-iodoalkynes in good to excellent yields under mild
conditions.
J. Yan, J. Li, D. Cheng, Synlett, 2007, 2442-2444.
Phenyliodonium ylides provide easy access to various 1,1-cyclopropane diesters
using rhodium or copper catalysis and are safer and convenient alternatives to
the corresponding diazo compounds. Moreover, the iodonium ylide of dimethyl
malonate was obtained in 78% yield using improved conditions that involve a
simple filtration step to isolate the desired product.
S. R. Goudreau, D. Marcoux, A. B. Charette, J. Org. Chem., 2009,
74, 470-473.
