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Chemicals >> Oxidizing Agents >> Hypervalent Iodine Compounds

Iodosobenzene bis(trifluoroacetate), bis(trifluoroacetoxy)iodobenzene, PIFA

Recent Literature

Oxidative deprotection of several dithiane-containing alkaloids in the presence of bis(trifluoroacetoxy)iodobenzene and a nonchromatic purification cleanly generates the corresponding ketoamines. The described procedure is ideal for labile alkaloids.
F. F. Fleming, L. Funk, R. Altundas, Y. Tu, J. Org. Chem., 2001, 66, 6502 - 6504.

A metal-free esterification of a broad range of alkynes with alcohols in the presence of phenyliodine bis(trifluoroacetate) produces esters in good yields via carbon triple bond cleavage. The transformation proceeds via hydroxyethanones and ethanediones as intermediates and exhibits a broad substrate scope and good functional group tolerance.
Q. Jiang, A. Zhao, B. Xu, J. Jia, X. Liu, C. Guo, J. Org. Chem., 2014, 79, 2709-2715.

The use of phenyliodine(III) bis(trifluoroacetate) enables a facile and direct oxidation of readily available β-ketoamides to provide vicinal tricarbonyl amides in good yields. This approach is a valuable addition to the group of traditional methods already available.
Y. Liu, Z. Zhang, Y. Wan, G. Zhang, Z. Li, J. Bi, N. Ma, T. Liu, Q. Liu, J. Org. Chem., 2017, 82, 3901-3907.

Lewis bases catalyze vicinal dioxygenation of olefins with hypervalent iodine reagents under mild conditions. The reaction tolerates various functional groups.
L. Pan, Z. Ke, Y.-Y. Yeung, Org. Lett., 2021, 23, 8174-8178.

An efficient, metal and base-free, chemoselective reaction of boronic acids with cyanamidyl/arylcyanamidyl radicals provides primary aryl-, heteroaryl-, and alkyl amines at ambient temperature within 1 h. The reaction is mediated by PIFA and NBS.
N. Chatterjee, M. Arfeen, P. V. Bharatam, A. Goswami, J. Org. Chem., 2016, 81, 5120-5127.

An oxidative deprotection of p-methoxy benzyl (PMB) ethers was achieved using a nitroxyl radical catalyst with electron-withdrawing ester groups adjacent to the nitroxyl group in the presence of 1 equiv of PIFA as co-oxidant. The corresponding carbonyl compounds were obtained in the presence of an excess of PIFA.
S. Hamada, K. Sugimoto, E. E. Elboray, T. Kawabata, T. Furuta, Org. Lett., 2020, 22, 5486-5490.

A microwave-assisted, metal-free direct decarboxylative elimination of arylacetic acids in the presence of PIFA as oxidant readily provides alkenes in good yields.
S.-W. Wu, J.-L. Liu, F. Liu, Org. Lett., 2016, 18, 1-3.

A new and convenient one-pot catalytic addition-elimination reaction converted a range of (E)-3-butenoic acids into the corresponding butenolides in good yields in the presence of 5 mol % diphenyl diselenide and [bis(trifluoroacetoxy)iodo]benzene in acetonitrile.
D. M. Browne, O. Niyomura, T. Wirth, Org. Lett., 2007, 9, 3169-3171.

Desilylative acetoxylation of (trimethylsilyl)arenes can be performed in the presence of 5 mol % of Pd(OAc)2 and PhI(OCOCF3)2 (1.5 equiv) in AcOH at 80°C for 17 h providing acetoxyarenes in very good yields. The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyl)arenes to phenols by successive acetoxylation and hydrolysis.
K. Gondo, J. Oyamada, T. Kitamura, Org. Lett., 2015, 17, 4778-4781.

Fluorination of styrene derivatives with a reagent system composed of μ-oxo-bis[trifluoroacetato(phenyl)iodine] or PhI(OCOCF3)2 and a pyridine·HF complex gave the corresponding (2,2-difluoroethyl)arenes in good yields. Catalytic conditions using 4-iodotoluene as a catalyst and m-CPBA as a terminal oxidant are possible.
T. Kitamura, K. Muta, J. Oyamada, J. Org. Chem., 2015, 80, 10431-10436.

PIFA mediates a nitration of aryl amines in the presence of MeNO2 as solvent and H2O as cosolvent via NO2 transfer. Using H2O as the solvent, the C(sp2)-H functionalization shifts to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.
C. Mudithanapelli, L. P. Dhorma, M.-h. Kim, Org. Lett., 2019, 21, 3098-3102.

The hypervalent iodine reagent PhI(OTf)2, generated in situ, has been successfully utilized in a metal-free intramolecular oxidative cyclization of N-styrylbenzamides. In remarkably short reaction times, the desired 2,5-disubstituted oxazoles were isolated in high yields.
C. Hempel, B. J. Nachtsheim, Synlett, 2013, 24, 2119-2123.

A mild, oxidative cycloisomerization of cis-enynols using a combination of a hypervalent iodine(III) reagent, molecular iodine, and a base offers an efficient synthesis of 2-acyl furans with diverse substitution patterns in a regioselective manner. A mechanistic proposal for these transformations involving alkyne activation by trifluoroacetylhypoiodite generated in situ is presented.
X. Du, H. Chen, Y. Chen, J. Chen, Y. Liu, Synlett, 2011, 1010-1014.

Various 5-aryl-2-methyltetrazoles and 5-aryl-2-benzyltetrazoles were directly prepared in good yields under transition metal-free and mild conditions by the reaction of aromatic aldehydes with methylhydrazine and benzylhydrazine, followed by treatment with di-tert-butyl azodicarboxylate and [bis(trifluoroacetoxy)iodo]benzene in a mixture of dichloromethane and 2,2,2-trifluoroethanol at room temperature.
T. Imai, R. Harigae, K. Moriyama, H. Togo, J. Org. Chem., 2016, 81, 3975-3980.

An intramolecular oxidative S-N bond formation of imidoyl thioureas mediated by phenyliodine(III) bis(trifluoroacetate) enables an efficient, metal-free synthesis of 3-substituted-5-arylamino-1,2,4-thiadiazoles. The protocol offers broad substrate scope, very short reaction times and very good yields.
A. Mariappan, K. Rajaguru, N. M. Chola, S. Muthusubramanian, N. Bhuvanesh, J. Org. Chem., 2016, 81, 6573-6579.

The use of PIFA {[bis(trifluoroacetoxy)iodo]benzene} or quinones enables a cyclization of 2-vinylanilines to provide various indoles under mild conditions in good yields.
M. Wu, R. Yan, Synlett, 2017, 28, 729-733.

Various N-arylated and N-alkylated indoles and pyrrole-fused aromatic compounds were synthesized by a phenyliodine bis(trifluoroacetate) (PIFA)-mediated intramolecular cyclization.
Y. Du, R. Liu, G. Linn, K. Zhao, Org. Lett., 2006, 8, 5919-5922.

The hypervalent iodine reagent PIFA promotes the efficient intramolecular electrophilic cyclization of easily accessible alkynylamides and alkynyl carboxylic acids, leading to pyrrolidinone and lactone skeletons, respectively. A synthetic study and a mechanistic proposal for these transformations are presented.
I. Tellitu, S. Serna, m. T. Herrero, I. Moreno, E. Domínguez, R. SanMartin, J. Org. Chem., 2007, 72, 1526-1529.

A general and efficient reaction of readily available N-methyl-N-phenylcinnamamides with phenyliodine bis(trifluoroacetate) (PIFA) in the presence of Lewis acids provides various 3-arylquinolin-2-one compounds in good yields. This novel approach features not only metal-free oxidative C(sp2)-C(sp2) bond formation but also an exclusive 1,2-aryl migration.
L. Liu, H. Lu, H. Wang, C. Yang, X. Zhang, D. Zhang-Negrerie, Y. Du, K. Zhao, Org. Lett., 2013, 15, 2903-2909.

The use of [bis(trifluoroacetoxy)iodo]benzene as stoichiometric oxidant and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as organocatalyst enables a convenient oxidation of isochromans. A further reaction with grignard reagents or amides affords the corresponding isochroman derivatives.
W. Muramatsu, K. Nakano, Org. Lett., 2014, 16, 2042-2045.

The biologically important 1,2,4-triazolo[1,5-a]pyridines were readily synthesized from N-(pyridin-2-yl)benzimidamides via PIFA-mediated intramolecular annulation via a direct metal-free oxidative N-N bond formation in short reaction times and high yields.
. Zheng, S. Ma, L. Tang, D. Zhang-Negrerie, Y. Du, K. Zhao, J. Org. Chem., 2014, 79, 4687-4693.

A facile and effective alkoxylation of quinoxalin-2(1H)-ones with primary or secondary alcohols via cross-dehydrogenative coupling under catalyst-free conditions provides 3-alkoxylquinoxalin-2(1H)-ones in very good yields in the presence of PhI(OTFA)2 as oxidant.
Q. Yang, X. Han, J. Zhao, H.-Y. Zhang, Y. Zhang, J. Org. Chem., 2019, 84, 11417-11424.

A low-temperature, protecting-group-free oxidation of 2-substituted anilines with PIFA in the presence of an acid generates an electrophilic N-aryl nitrenoid intermediate that can engage in C-NAr bond formation to construct functionalized N-heterocycles, such as spirocyclic- or bicyclic 3H-indoles or benzazepinones.
T. Deng, W. Mazumdar, R. L. Ford, N. Jana, R. Izar, D. J. Wink, T. G. Driver, J. Am. Chem. Soc., 2020, 142, 4456-4463.