Iodosobenzene Diacetate, Phenyliodonium Diacetate, PIDA
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.
Selective syn and anti diacetoxylations of alkenes have been achieved using a PhI(OAc)2/BF3·OEt2 system in the presence and absence of water, respectively. A broad range of substrates including electron-deficient alkenes furnishes the desired products in good to excellent yields and diastereoselectivity. This novel methodology provides an alternative approach for the preparation of various 1,2-diols.
W. Zhong, J. Yang, X. Meng, Z. Li, J. Org. Chem., 2011, 76, 9997-10004.
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.
In a rhenium-catalyzed oxyalkylation of alkenes, hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were not only an oxygenation source but also an alkylation source via decarboxylation. The reaction offers a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates.
Y. Wang, L. Zhang, Y. Yang, P. Zhang, Z. Du, C. Wang, J. Am. Chem. Soc., 2013, 135, 18048-18051.
Half-sandwich ruthenium complexes activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. Propargylic alcohols can be converted to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively.
M. Zeng, S. B. Herzon, J. Org. Chem., 2015, 80, 8604-8618.
An oxidative decarboxylation of β,γ-unsaturated carboxylic acids mediated by PhI(OAc)2 gives the corresponding allylic acetates. In addition, a decarboxylative C-N bond formation was achieved. Mechanistic studies suggest an unique reactivity of hypervalent iodine reagents in this ionic oxidative decarboxylation.
K. Kiyokawa, S. Yahata, T. Kojima, S. Minakata, Org. Lett., 2014, 16, 4646-4649.
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.
A direct conversion of a wide range of aliphatic, benzylic, heteroaromatic, allylic, and propargyl alcohols into nitriles with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), iodosobenzene diacetate, and ammonium acetate as a nitrogen source proceeds through an oxidation-imination-aldimine oxidation sequence in situ. Highly chemoselective ammoxidation of primary alcohols in the presence of secondary alcohols was also achieved.
J.-M. Vatèle, Synlett, 2014, 25, 1275-1278.
The use of diacetoxyiodobenzene in the presence of an ionic liquid enables a facile one-pot synthesis of a series of amides from aldehydes and amines at ambient temperature.
V. Prasad, R. R. Kale, B. B. Mishra, D. Kumar, V. K. Tiwari, Org. Lett., 2012, 14, 2936-2939.
A copper-catalyzed cross-dehydrogenative coupling reaction between N-hydroxyphthalimide and aldehydes using PhI(OAc)2 as an oxidant enables a synthesis of NHPI esters in good yields in water. This facile and efficient method is eco-friendly and offers mild conditions, short reaction time, and broad substrate scope.
Z. Guo, X. Jiang, C. Jin, J. Zhou, B. Sun, W. Su, Synlett, 2017, 28, 1321-1326.
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.
The use of PhI(OAc)2 enables an efficient access to α,α′-diacetoxy ketones has from ethynylcarbinols. Glycerol derivatives can be easily synthesized in good yields via a one-pot reaction. A plausible mechanism is proposed.
Q.-R. Liu, C.-X. Pan, X.-P. Ma, D.-L. Mo, G.-F. Su, J. Org. Chem., 2015, 80, 6496-6501.
Phenyliodonium diacetate mediates a synthesis of α-oxygenated ketones from styrenes in the presence of molecular oxygen and N-hydroxyphthalimide or N-hydroxybenzotriazole under metal-free conditions. The present method is applicable for wide range of styrenes with various functional groups.
S. Samanta, R. R. Donthiri, C. Ravi, S. Adimurthy, J. Org. Chem., 2016, 81, 3457-3463.
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.
A one-pot two-step sequence involving an oxidation/imine-iminium formation/reduction allowed the N-alkylation of amines by alcohols. Optically active alcohols and amines can be converted without any epimerization.
C. Guérin, V. Bellosta, G. Guillamot, J. Cossy, Org. Lett., 2011, 13, 3478-3481.
An oxidation/imine-iminium formation/reduction cascade using TEMPO-BAIB-HEH-Brønsted acid catalysis in DMPU as solvent enables a mild and atom-economical nonepimerizing chemo- and enantioselective N-alkylating procedure of amines with alcohols.
I. A. Khan, A. K. Saxena, J. Org. Chem., 2013, 78, 11656-11669.
Trimethylchlorosilane was used as chlorine source for the α-chlorination of 1,3-dicarbonyl compounds with phenyliodonium diacetate as oxidant at room temperature to provide α-monochlorinated products in good yield. TMSBr could be used to form monobromide products.
S. Chong, Y. Su, L. Wu, W. Zhang, J. Ma, X. Chen, D. Huang, K.-H. Wang, Y. Hu, Synthesis, 2016, 48, 1359-1370.
A mild and rapid formal electrophilic α-azidation of 1,3-dicarbonyl compounds using commercially available Bu4NN3 as the azide source is mediated by (diacetoxyiodo)benzene. The reaction conditions are Bäcklund to the ones employed in analogous halogenations with Et4NX (X = Cl, Br, I).
M. J. Galligan, R. Akula, H. Ibrahim, Org. Lett., 2014, 16, 600-603.
A tandem metal-free oxidative aryl migration/C-C bond-cleavage reaction, mediated by hypervalent iodine reagent, provides straightforward access to important α-ketoamide and α-ketoester derivatives from readily available acrylic derivatives via a concerted process of 1,2-aryl shift concomitant with C-C bond cleavage.
L. Liu, L. Du, D. Zhang-Negrerie, Y. Du, K. Zhao, Org. Lett., 2014, 16, 5772-5775.
A metal-free PhI(OAc)2 mediated nitrogenation of alkenes via C=C bond cleavage using inorganic ammonia salt as nitrogen source under mild conditions affords nitriles in good yields. The method offers mild reaction conditions, operational simplicity, and use of an ammonium salt as nitrogen source. A plausible reaction mechanism is proposed.
J.-H. Xu, Q. Jiang, C.-C. Guo, J. Org. Chem., 2013, 78, 11881-11882.
The combination of hypervalent iodine(III) and TMSN3 promotes an oxidative cleavage of C-C double bonds of enamides under an air atmosphere. This method exhibits good functional group tolerance, broad substrate scope and mild conditions. The reaction also offers an approach to cyanobenzamides with synthetic potential for the preparation of industrial and pharmaceutical nitrogen- and oxygen-containing molecules.
G. Liu, Y. Li, J. Sheng, X.-S. Wang, Synthesis, 2017, 49, 3968-3974.
Gold-catalyzed oxidative cross-coupling of alkynes to unsymmetrical diynes has been achieved in the presence of 1,10-Phen as ligand and PhI(OAc)2 as oxidant giving the desired cross-coupled conjugated diynes in excellent heteroselectivity (>10:1), in good to excellent yields, and with large substrate tolerability.
H. Peng, Y. Xi, N. Ronaghi, B. Dong, N. G. Akhmedov, X. Shi, J. Am. Chem. Soc., 2014, 136, 13174-13177.
In a palladium-catalyzed intermolecular aminocarbonylation of alkenes, the use of hypervalent iodine reagent can accelerate the reaction. The current transformation presents a convenient method to generate β-amino acid derivatives from simple alkenes.
J. Cheng, X. Qi, M. Li, P. Chen, G. Liu, J. Am. Chem. Soc., 2015, 137, 2480-2483.
In a radical-mediated strategy for β C-H amination of alcohols, imidates as radical relay chaperones serve as traceless directors that facilitates selective C-H functionalization via 1,5-hydrogen atom transfer (HAT) and enable net incorporation of ammonia at the β carbon. A streamlined protocol enables rapid conversion of alcohols to their β-amino analogs (via in situ conversion of alcohols to imidates, directed C-H amination, and hydrolysis).
E. A. Wappes, K. M. Nakafuku, D. A. Nagib, J. Am. Chem. Soc., 2017, 139, 10204-10207.
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.
An oxidative cyclization of β-substituted β,γ-unsaturated carboxylic acids using a hypervalent iodine reagent provides 4-substituted furan-2-ones. The use of the highly electrophilic PhI(OTf)2, which is in situ prepared from PhI(OAc)2 and Me3SiOTf, is crucial. Depending on the substitution pattern at the α-position of the substrates, furan-2(5H)-ones or furan-2(3H)-ones are produced.
K. Kiyokawa, K. Takemoto, S. Yahata, T. Kojima, S. Minakata, Synthesis, 2017, 49, 2907-2912.
In the presence of 1.1 equiv of (Diacetoxyiodo)benzene (PIDA) and suitable halogen sources, a variety of olefins underwent haloamidation, haloetherification, and halolactonization to the corresponding 1,2-bifunctional cyclic skeletons in very good isolated yields. Subsequent mild nucleophilic substitution gives key intermediates for biologically interesting compounds in high yields.
G.-Q. Liu, Y.-M. Li, J. Org. Chem., 2014, 79, 10094-10109.
An efficient synthesis of indolines compounds from picolinamide (PA)-protected β-arylethylamine substrates via palladium-catalyzed intramolecular amination of ortho-C(sp2)-H bonds features high efficiency, low catalyst loadings, mild operating conditions, and the use of inexpensive reagents.
G. He, C. Lu, Y. Zhao, W. A. Nack, G. Chen, Org. Lett., 2012, 14, 2936-2939.
A Pd(II)-catalyzed intramolecular C-H amination of 2-pyridinesulfonyl-protected phenethylamine derivatives using PhI(OAc)2 as a bystanding oxidant provides access to various substituted indoline derivatives in good yields. The use of the 2-pyridinesulfonyl protecting group enables a facile deprotection following C-H functionalization.
T.-S. Mei, D. Leow, H. Xiao, B. N. Laforteza, J.-Q. Yu, Org. Lett., 2013, 15, 3058-3061.
3-Monofunctionalized 2-oxindoles were conveniently synthesized from reactions between an anilide and phenyliodine(III) diacetate (PIDA) through hypervalent iodine mediated C(sp2)–C(sp2) bond formation followed by a subsequent deacylation. This metal-free method provides direct access to interesting oxindole intermediates, as exemplified by the total synthesis of horsfiline.
J. Lv, D. Zhang-Negrerie, J. Deng, Y. Du, K. Zhao, J. Org. Chem., 2014, 79, 1111-1119.
2-Benzyl-N-tosylbenzamides and related substrates undergo copper-catalyzed intramolecular benzylic sulfamidation to provide N-arylsuflonyl-1-arylisoindolinones.
R. B. Bedford, J. G. Bowen, C. Méndez-Gálvez, J. Org. Chem., 2017, 82, 1719-1725.
The use of Cu(OAc)2 as the catalyst in the presence of PhI(OAc)2 and K3PO4 enables an amination of aliphatic C-H bonds of N-alkylamidines to yield dihydroimidazoles and tetrahydropyrimidines. A subsequent hydride reduction gives the corresponding diamines.
H. Chen, S. Synjaya, Y.-F. Wang, S. Chiba, Org. Lett., 2013, 15, 212-215.
A metal-free catalytic strategy for the facile synthesis of biologically relevant indolizines and imidazopyridines scaffolds is promoted by amine and N-heterocyclic carbene (NHC) relay catalysis via Michael addition-[3 + 2] fusion of simple azaarenes and α,β-unsaturated aldehydes.
H. Li, X. Li, Y. Yu, J. Li, Y. Liu, H. Li, W. Wang, Org. Lett., 2017, 19, 2010-2013.
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.
Palladium-catalyzed intramolecular amination of unactivated C-H bonds at the γ and δ positions of picolinamide (PA) protected amine substrates enables the synthesis of azetidine, pyrrolidine, and indoline compounds. The method features relatively low catalyst loading, use of inexpensive reagents, convenient operating conditions and predictable selectivities.
G. He, Y. Zhao, S. Zhang, C. Lu, G. Chen, J. Am. Chem. Soc., 2012, 134, 3-6.
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.
A broad range of functionalized oxazoles were synthesized in good yields from enamides via phenyliodine diacetate (PIDA)-mediated intramolecular cyclization. The oxidative carbon-oxygen bond formation process is heavy-metal-free.
Y. Zheng, X. Li, C. Ren, D. Zhang-Negrerie, Y. Du, K. Zhao, J. Org. Chem., 2012, 77, 10353-10361.
Hypervalent iodine compounds enable Pd-catalyzed acetoxylative, alkoxylative, and hydroxylative cycloisomerizations of homoallenyl amides to give three different types of polysubstituted 2-aminofurans in promising yields at room temperature.
C. Cheng, S. Liu, G. Zhu, J. Org. Chem., 2015, 80, 7604-7612.
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.
A convenient metal-free cyclization of ortho-hydroxystilbenes into 2-arylbenzofurans and 2-arylnaphthofurans is mediated by hypervalent iodine reagents. Using stoichiometric (diacetoxyiodo)benzene in acetonitrile, desired products can be isolated in good yields.
F. V. Singh, T. Wirth, Synthesis, 2012, 44, 1171-1177.
Pd(II)-catalyzed C-H activation of phenylacetic acids followed by an intramolecular C-O bond formation afforded benzofuranones. A modified reaction provides the first example of enantioselective C-H functionalizations through Pd(II)/Pd(IV) redox catalysis.
X.-F. Cheng, Y. Li, Y.-M. Su, F. Yin, J.-Y. Wang, J. Sheng, H. U. Vora, X.-S. Wang, J.-Q. Yu, J. Am. Chem. Soc., 2013, 135, 1236-1239.
A fast and simple reaction of amidines gave benzimidazoles via iodine(III)-promoted oxidative C(sp3)-C(sp2) bond formation in nonpolar solvents, whereas the use of polar solvents favoured a C(sp2)-N bond formation to yield quinazolines. Further selective synthesis of quinazolines in polar solvent was realized using TEMPO as catalyst and K2S2O8 as the oxidant. No metal, base, or other additives were needed.
J.-P. Lin, F.-H. Zhang, Y.-Q. Long, Org. Lett., 2014, 16, 2822-2825.
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 copper-catalyzed cycloamination of α-Csp3-H bond of N-aryl ketimines with sodium azide provides an efficient access to quinoxalines. The reaction features mild conditions and a broad functional group tolerance.
T. Chen, X. Chen, J. Wei, D. Lin, Y. Xie, W. Zeng, Org. Lett., 2016, 18, 2078-2081.
Cyclization of 2-aminobenzamides and aldehydes catalyzed by p-toluenesulfonic acid followed by an efficient PIDA-mediated oxidative dehydrogenation enables the synthesis of various 4(3H)-quinazolinones - including quinazolinones bearing an N-alkoxy substituent. The method offers mild reaction conditions.
R. Cheng, T. Guo, D. Zhang-Negrerie, Y. Du, K. Zhao, Synthesis, 2013, 45, 2998-3006.
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.
A rhodium-catalyzed transfer of carbamates to sulfoxides enables a convenient synthesis of N-protected sulfoximines under mild conditions. Sulfoximines, including 4-membered thietane-oximines, bearing Boc and Cbz groups are readily deprotected.
M. Zenzola, R. Doran, R. Luisi, J. A. Bull, J. Org. Chem., 2015, 80, 6391-6399.