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Potassium peroxydisulfate

See also: ammonium peroxydisulfate, choline peroxydisulfate, sodium peroxydisulfate, tetrabutylammonium peroxydisulfate

Recent Literature

The use of potassium persulfate enables an aerobic oxidation of benzyl substrates to provide aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids under mild conditions in the presence of pyridine. Neither transition metals nor halogens are required as additives.
Y. Hu, L. Zhou, W. Lu, Synthesis, 2017, 49, 4007-4016.

The use of visible-light-induced silver catalysis enables a controlled singlet-oxygen-mediated selective C-S bond cleavage reaction of benzyl thiols to afford carbonyl compounds.
B. Hong, K. C. C. Aganda, A. Lee, Org. Lett., 2020, 22, 4395–4399.

Various aryl ketone derivatives react readily with DMSO under transition metal-free reaction condition, producing the α,β-unsaturated carbonyl compounds in good yields. This direct α-Csp3-H methylenation offers wide substrate scope and provides an efficient and expeditious approach to an important class of α,β-unsaturated carbonyl compounds.
Y.-F. Liu, P. Yi Ji, J.-W. Xu, Y.-Q. Hu, Q. Liu, W.-P. Luo, C.-C. Guo, J. Org. Chem., 2017, 82, 7161-7164.

A Fe-mediated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution provides an efficient and expeditious approach to α,β-unsaturated carbonyl compounds. This transformation offers a wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents. Mechanism studies suggest that a free radical pathway is involved.
Q. Jiang, J. Jia, B. Xu, A. Zhao, C.-C. Guo, J. Org. Chem., 2015, 80, 3586-3596.

The combination of potassium persulfate and ambient air enables a catalyst- and transition-metal-free oxidation of various internal alkynes to the corresponding 1,2-diketones in very good yields. Mechanistic studies indicate a radical process with both the persulfate salt and molecular oxygen as source of the incorporated oxygen atoms.
D. Shen, H. Wang, Y. Zheng, X. Zhu, P. Gong, B. Wang, J. You. Y. Zhao, M. Chao, J. Org. Chem., 2021, 86, 5354-5361.

With K2S2O8 as the oxidant and AgNO3 as the catalyst, direct decarboxylative radical allylation of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in good yields under mild conditions. This site-specific allylation method exhibits wide functional group compatibility.
L. Cui, H. Chen, C. Liu, C. Li, Org. Lett., 2016, 18, 2188-2191.

A silver-promoted oxidative ring opening/alkynylation of cyclopropanols with ethynylbenziodoxolones (EBX) enables the formation of alkylated alkynes. Control experiments support a radical mechanism.
C.-Y. Wang, R.-J. Song, Y.-X. Xie, J.-H. Li, Synthesis, 2016, 48, 223-230.

The generation of a tribromomethyl radical from tetrabromomethane (CBr4) with the assistance of a persulfate salt (K2S2O8) enables a single step conversion of terminal alkynes to gem-dibromoenones in the presence of water. The reaction features readily available chemicals, a broad substrate scope, a green solvent, and mild reaction conditions.
X. Zeng, Y. Xu, J. Liu, Y. Deng, Org. Lett., 2021, 23, 9058-9062.

A cobalt-catalyzed allylation of amides with styrenes, in which DMSO was used as both the solvent and the α-methylene source, provides privileged allylic amines in high yields, and selectivity for the (E)-isomer of the linear product.
X. Zhang, Z. Zhou, H. Xu, X. Xu, X. Yu, W. Yi, Org. Lett., 2019, 21, 7248-7253.

A K2S2O8-mediated transition metal-free oxidative cross-coupling reaction of activated olefins with N-alkyl amides provides N-allylic amides in good yield.
M. Li, L. Zhang, L. Ma, Y. Chen, J. Org. Chem., 2021, 86, 3989-3998.

A coupling of substituted Hantzsch esters or Meyer nitriles with benziodoxole-activated alkynes provides products containing Csp3-Csp bonds involving primary, secondary, and tertiary carbon centers in good yields. K2S2O8 was the optimum radical initiator in this reaction.
X. Liu, R. Liu, J. Dai, X. Cheng, G. Li, Org. Lett., 2018, 20, 6906-6909.

Visible-light-driven hydroacylations and epoxyacylations in water using methylene blue as photoredox catalyst and persulfate as oxidant deliver ketones and epoxyketones from a range of aromatic and aliphatic aldehydes as well as conjugated and nonconjugated olefins as abundant and inexpensive chemical feedstocks.
G. F. P. de Souza, J. A. Bonacin, A. G. Salles, Jr., J. Org. Chem., 2018, 83, 8331-8340.

Under very mild oxidative conditions, 1,4-dihydropyridines (DHPs), derived from aldehydes, generate C(sp3)-radicals that couple with halogen radicals, which are generated from inexpensive halogen sources (NaBr, NaI, or HCl), to yield alkyl halides. The reaction tolerates a broad range of functional groups and achieves excellent site selectivity.
S. Liang, T. Kumon, R. A. Angnes, M. Sanchez, B. Xu, G. B. Hammond, Org. Lett., 2019, 21, 3848-3854.

With AgNO3 as the catalyst and K2S2O8 as the oxidant, an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous MeCN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed.
C. Liu, X. Wang, Z. Li, L. Cui, C. Li, J. Am. Chem. Soc., 2015, 137, 9820-9823.

In a catalytic decarboxylative nitrogenation, a series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K2S2O8 as the oxidant and PhSO2N3 as the nitrogen source via an alkyl radical process.
Y. Zhu, X. Liu, X. Wang, X. Huang, T. Shen, Y. Zhang, X. Sun, M. Zou, S. Song, N. Jiao, Org. Lett., 2015, 17, 4702-4705.

In the presence of AgNO3 as the catalyst and K2S2O8 as the oxidant, reactions of aliphatic carboxylic acids with (bpy)Cu(CF3)3 and ZnMe2 in aqueous acetonitrile at 40°C provide the corresponding decarboxylative trifluoromethylation products in good yield. The protocol is applicable to various primary and secondary alkyl carboxylic acids and exhibits wide functional group compatibility.
X. Tan, Z. Liu, H. Shen, P. Zhang, Z. Zhang, C. Li, J. Am. Chem. Soc., 2017, 139, 12430-12433.

The trifluoromethylation of aldehydes with (bpy)Cu(CF3)3, Et3SiH, and K2S2O8 in aqueous acetone at room temperature provides the corresponding trifluoromethyl ketones in satisfactory yields. The protocol is applicable to both aliphatic and aromatic aldehydes and exhibits wide functional group compatibility. A mechanism involving Cu(II)-mediated trifluoromethylation of acyl radicals is proposed.
P. Zhang, H. Shen, L. Zhu, W. Cao, C. Li, Org. Lett., 2018, 20, 7062-7065.

A direct Csp3-H bond oxidative thioesterification of methyl ketones with aromatic thiols/disulfides is promoted by TBAI/K2S2O8 to provide functionalized α-ketothioesters. This efficient reaction offers large-scale applicability and broad functional group tolerance.
B. Hu, Pan Zhou, Q. Zhang, Y. Wang, S. Zhao, L. Lu, S. Yan, F. Yu, J. Org. Chem., 2018, 83, 14978-14986.

A 1,2-thiocyanatosulfonation of terminal alkynes with NH4SCN and sulfonyl hydrazides provides (E)-β-(thiocyanato)vinyl sulfones via a radical pathway. This metal-free reaction offers mild conditions, readily available reagents, a broad substrate scope, good functional group compatibility, and excellent stereoselectivity.
M. Zhang, X. Zeng, Org. Lett., 2021, 23, 3326-3330.

Various anilides have been directly ortho-acetoxylated with acetic acid as the acetate source and K2S2O8 as the oxidant in the presence of Pd(OAc)2 as catalyst. The amide group is an elegant directing group to convert aromatic sp2 C-H bonds into C-O bonds.
G.-W. Wang, T.-T. Yuan, X.-L. Wu, J. Org. Chem., 2008, 73, 4717-4720.

An iron-promoted oxidative tandem alkylation/cyclization of ynones with 4-alkyl-substituted 1,4-dihydropyridines provides 2-alkylated indenones with excellent selectivity under mild conditions. The process occurs via oxidative homolysis of a C-C σ-bond in 1,4-dihydropyridines to generate an alkyl radical followed by its addition to the C-C triple bond and an intramolecular cyclization.
F.-T. Xiong, B.-H. He, Y. Liu, Q. Zhou, J.-H. Fan, J. Org. Chem., 2022, 87, 8599-8610.

A pH-controlled polarity umpolung strategy enables a simple intramolecular aroylation of electron-rich arenes under mild conditions to provide different fluorenones, which are important building blocks for biological applications. Unlike previous acylation reactions involving nucleophilic aroyl radicals, this approach likely relies on in situ generated electrophilic aroyl radicals.
J. K. Laha, U. Gulati, Saima, T. Schulte, M. Breugst, J. Org. Chem., 2022, 87, 6638-6656.

A copper(II)-catalyzed oxidative cyclization of enamides gives oxazoles via vinylic C-H bond functionalization at room temperature. Various 2,5-disubstituted oxazoles bearing aryl, vinyl, alkyl, and heteroaryl substituents could be synthesized in good yields. This reaction protocol is complementary to a previously reported iodine-mediated cyclization of enamides to afford 2,4,5-trisubstituted oxazoles.
C. W. Cheung, S. L. Buchwald, J. Org. Chem., 2012, 77, 7526-7537.

A highly efficient method for the synthesis of oxazole derivatives from simple amides and ketones proceeds through a C-N bond formation followed by a C-O bond formation closing the ring. Because of the simple and readily available starting materials, easy operation, and high bioactivity of oxazoles, this strategy can be broadly applied to medicinal chemistry.
M. Zhang, L. Huang, H. Huang, X. Li, W. Wu, H. Jiang, Org. Lett., 2014, 16, 5906-5909.

A facile and practical TBAI-catalyzed reaction between N-tosyl hydrazones and sulfur provides 1,2,3-thiadiazoles in good yields under metal-free conditions. This procedure serves as an improvement for the Hurd-Mori reaction.
J. Chen, Y. Jiang, J.-T. Yu, J. Cheng, J. Org. Chem., 2016, 81, 271-275.

A highly efficient reaction of readily available tosylhydrazones with ammonium thiocyanate in ecofriendly EtOH as the solvent provides 1,2,3-thiadiazoles in very good yields at room temperature. The reaction shows a wide scope of substrates and good functional-group tolerance.
Y. Lu, Y. Sun, A. Abdukader, C. Liu, Synlett, 2021, 32, 1044-1048.

A palladium-catalyzed ring-opening reaction of 2H-azirines with hydrazones provides polysubstituted pyrazoles with a wide substrate scope.
J. Shao, K. Shu, S. Liu, H. Zhu, J. Zhang, C. Zhang, L.-H. Zeng, L. Zeng, W. Chen, J. An, Synlett, 2021, 32, 316-320.

An efficient and versatile Pd(II)-catalyzed oxidative three-component cascade reaction of diverse amines, alkyne esters, and alkenes enables the direct synthesis of diverse 2,3,4-trisubstituted pyrroles with broad functional group tolerance and in good to excellent yields.
X. Zhang, X. Xu, G. Chen, W. Yi, Org. Lett., 2016, 18, 4864-4867.

A palladium-catalyzed C-C bond activation of cyclopropenone and concomitant carbonylative amination provides maleimides. Eliminated carbon monoxide from the cyclopropenone is efficiently recaptured in the catalytic cycle for the formation of maleimides.
T. Nanda, P. C. Ravikumar, Org. Lett., 2020, 22, 1368-1374.

A regioselective Minisci monoacylation of electron-rich pyrroles under silver-free neutral conditions provides the desired products without polymerization of pyrroles.
J. K. Laha, M. K. Hunjan, S. Hegde, A. Gupta, Org. Lett., 2020, 22, 1442-1447.

A copper-catalyzed three-component reaction of methyl ketones, organic azides, and DMF as one-carbon (C1) donor provides 4-acyl-1,2,3-triazoles in good yields. The transformation proceeds via an oxidative C-H/C-H cross-dehydrogenative coupling followed by an oxidative 1,3-dipolar cycloaddition.
Y. Liu, G. Nie, Z. Zhou, L. Jia, Y. Chen, J. Org. Chem., 2017, 82, 9198-9203.

An oxidative annulation involving anilines, aryl ketones, and DMSO as a methine (=CH−) equivalent promoted by K2S2O8 provides 4-arylquinolines, whereas activation of acetophenone-formamide conjugates enables the synthesis of 4-arylpyrimidines.
S. D. Jadhav, A. Singh, Org. Lett., 2017, 19, 5673-5676.

A [3+1+1+1] annulation of arylamines, arylaldehydes and dimethyl sulfoxide (DMSO) provides 3-arylquinolines in very good yields. In this annulation, arylamines provide two carbon atoms and one nitrogen atom, arylaldehydes furnish one carbon atom, and DMSO provides two nonadjacent methines (=CH-).
T. Yang, H. Li, Z. Nie, M.-d. Su, W.-p. Luo, Q. Liu, C.-C. Guo, J. Org. Chem., 2022, 87, 2797-2808.

A TBAI/K2S2O8-promoted [4 + 2] annulation of ketene N,S-acetals, and N-tosylhydrazones provides a variety of trisubstituted pyridazines in good yields. The method offers a broad substrate scope and a good functional group tolerance.
Z. Liu, J. Lou, J. Xiao, Org. Lett., 2021, 23, 1606-1610.

The use of K2S2O8 enables a nontransition metal-catalyzed synthesis of 2-aryl benzothiazoles through oxidative condensation of benzothiazoles with aryl aldehydes or phenylglyoxylic acids.
Z. Yang, X. Chen, S. Wang, J. Liu, K. Xie, A. Wang, Z. Tan, J. Org. Chem., 2012, 77, 7086-7091.

Visible light mediates a transition-metal-free formation of benzothiazoles from thiobenzanilides in the presence of riboflavin as a photosensitizer and potassium peroxydisulfate as a sacrificial oxidizing agent. This methodology tolerates a broad range of functional groups and affords 2-substituted benzothiazoles in good yields under very mild conditions.
L. M. Bouchet, A. A. Heredia, J. E. Argüello, L. C. Schmidt, Org. Lett., 2020, 22, 610-614.

A Pd(II)-catalyzed C(sp3)-H/C(sp2)-H coupling/annulation of anilides and α-dicarbonyl compounds provides diverse N-acyl indoles with high functional group tolerance and excellent regioselectivity.
R. S. Thombal, Y. R. Lee, Org. Lett., 2020, 22, 3397-3401.

A convenient one-pot, three-component reaction of aryl ketones with 2-amino-N-heterocycles and dimethyl sulfoxide as a methylene donor provides 3-aroylimidazo[1,2-a]-N-heterocycles in good yields in the presence of K2S2O8 and a catalytic amount of I2.
Y. Zhang, R. Chen, Z. Wang, L. Wang, Y. Ma, J. Org. Chem., 2021, 86, 6239-6246.

The use of K2S2O8 and DMSO enables an efficient and transition-metal-free synthesis of 4-arylquinolines from readily available aryl alkynes and anilines with a diverse range of substitution patterns. DMSO acts as one carbon source, thus providing a highly atom-economical and environmentally benign approach for the synthesis of 4-arylquinolines.
M. Phanindrudu, S. B. Wakade, D. K. Tiwari, P. R. Likhar, D. K. Tiwari, J. Org. Chem., 2018, 83, 9137-9143.

A highly efficient and regioselective Co(III)-catalyzed C-H activation/cyclization of simple, cheap, and easily available anilines with alkynes enables a direct synthesis of a broad range of privileged quinolines. In this reaction, DMSO serves both as the solvent and a C1 building block.
X. Xu, Y. Yang, X. Zhang, W. Yi, Org. Lett., 2018, 20, 566-569.

An oxidative annulation involving anilines, aryl ketones, and DMSO as a methine (=CH−) equivalent promoted by K2S2O8 provides 4-arylquinolines, whereas activation of acetophenone-formamide conjugates enables the synthesis of 4-arylpyrimidines.
S. D. Jadhav, A. Singh, Org. Lett., 2017, 19, 5673-5676.

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.

A one-pot reaction cascade reaction enables a transition-metal-free construction of functionalized quinolines from readily available acetophenones and anthranils. The reaction involves in situ generation of α,β-unsaturated ketones from the acetophenone via one-carbon homologation by DMSO followed by the aza-Michael addition of anthranils and subsequent annulation. DMSO acts not only as solvent but also as one carbon source.
S. B. Wakade, D. K. Tiwari, P. S. K. P. Ganesh, M. Phanindrudu, P. R. Likhar, D. K. Tiwari, Org. Lett., 2017, 19, 4948-4951.

A silver-catalyzed method provides a practical, highly efficient, and straightforward route to substituted quinolin-2-ones or 3,4-dihydroquinolin-2-ones in one step through an intermolecular radical addition/cyclization in aqueous solution. A mechanism for the formation of quinolin-2-ones is proposed.
W.-P. Mai, G.-C. Sun, J.-T. Wang, G. Song, P. Mao, L.-R. Yang, J.-W. Yuan, Y.-M. Xiao, L.-B. Qu, J. Org. Chem., 2014, 79, 8094-8102.

An efficient metal-free tandem acylation/cyclization of alkynoates with aldehydes enables the synthesis of 3-acyl-4-arylcoumarins via addition of acyl radical to alkynes and a C-H bond functionalization to form two new C-C bonds simultaneously.
X. Mi, C. Wang, M. Huang, Y. Wu, Y. Wu, J. Org. Chem., 2015, 80, 148-155.

A transition-metal-free, K2S2O8-mediated intramolecular oxidative nitrogenation/oxygenation of C(sp3)-H in N-aryl benzylic amines followed by oxidation at the benzylic center provides an expedient access to quinazolin-4(3H)-ones, N-aryl-2-arylbenzimidazoles, and 4H-3,1-benzoxazin-4-ones.
J. K. Laha, K. S. S. Tummalapalli, A. Nair, N. Patel, J. Org. Chem., 2015, 80, 11351-11359.

A novel Pd-catalyzed cascade dehydrogenative cross-coupling/annulation reaction of N-alkoxybenzamides with β-keto esters enables the synthesis of isoquinolinone derivatives. A plausible mechanism involves α-C(sp2)-H activation and a Pd(II)/Pd(IV) catalytic cycle.
G.-D. Xu, Z.-Z. Huang, Org. Lett., 2017, 19, 6265-6267.

An oxidative cross-dehydrogenative coupling (CDC) strategy enables an efficient acylation of quinolines and isoquinolines with arylmethanols as the acylating agents. This C-aroylation reaction was carried out in the presence of K2S2O8 as oxidant and methyltrioctylammonium chloride (Aliquat 336) as transfer agent in MeCN at 80°C under transition-metal-free conditions.
M. Adib, R. Pashazadeh, S. Rajai-Daryasarei, R. Kabiri, S. J. A. Gohari, , Synlett, 2016, 27, 2241-2245.

Tetraethylammonium bromide catalyzes an intramolecular oxidative cyclization of O- or S-alkylated salicylic or thiosalicylic acid derivatives to access 4H-benzo[d][1,3]dioxin-4-ones or 4H-benzo[d][1,3]oxathiin-4-ones. While the reaction of salicylic acid derivatives proceeds through a radical pathway at 110 °C, the cyclization of the thiosalicylic acids runs at room temperature via an ionic pathway.
K. Manna, H. M. Begam R. Jana, Synthesis, 2023, 55, 1543-1552.

A scalable, direct functionalization of various quinones with several boronic acids proceeds readily at room temperature in an open flask using catalytic silver(I) nitrate in the presence of a persulfate co-oxidant. The scope with respect to quinones is broad, with a variety of alkyl- and arylboronic acids undergoing efficient cross-coupling.
Y. Fujiwara, V. Domingo, I. B. Seiple, R. Gianatassio, M. Del Bel, P. P. S. Baran, J. Am. Chem. Soc., 2011, 133, 3292-3295.

One-pot tandem Meyer-Schuster rearrangement of arylpropynols and successive radical cyclization with disulfides enables the synthesis of 2-sulfenylindenone derivatives in good yields. The reaction tolerates a number of functional groups.
X.-S. Zhang, J.-Y. Jiao, X.-H. Zhang, B.-L. Hu, X.-G. Zhang, J. Org. Chem., 2016, 81, 5710-5716.