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Review
. 2021 Dec 12;26(24):7523.
doi: 10.3390/molecules26247523.

Recent Advances in the Oxone-Mediated Synthesis of Heterocyclic Compounds

Helen A Goulart  1 , Daniela R Araujo  1 , Filipe Penteado  1 , Raquel G Jacob  1 , Gelson Perin  1 , Eder J Lenardão  1
Affiliations
Review

Recent Advances in the Oxone-Mediated Synthesis of Heterocyclic Compounds

Helen A Goulart et al. Molecules. .

Abstract

Oxone is a commercially available oxidant, composed of a mixture of three inorganic species, being the potassium peroxymonosulfate (KHSO5) the reactive one. Over the past few decades, this cheap and environmentally friendly oxidant has become a powerful tool in organic synthesis, being extensively employed to mediate the construction of a plethora of important compounds. This review summarizes the recent advances in the Oxone-mediated synthesis of N-, O- and chalcogen-containing heterocyclic compounds, through a wide diversity of reactions, starting from several kinds of substrate, highlighting the main synthetic differences, advantages, the scope and limitations.

Keywords: Oxone; green chemistry; heterocycles; oxidant.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Oxone-mediated synthesis of heterocyclic compounds.
Scheme 2
Scheme 2
Oxone/PhI-promoted annulation of N-substituted hydrazones 2.
Scheme 3
Scheme 3
Plausible reaction mechanism for the Oxone/PhI-promoted annulation process.
Scheme 4
Scheme 4
Oxone/CuBr-mediated synthesis of triazole-fused heterocycles 3.
Scheme 5
Scheme 5
Oxone-mediated synthesis of oxindoles 6.
Scheme 6
Scheme 6
Oxone-mediated synthesis of 2-substituted benzimidazoles 10.
Scheme 7
Scheme 7
Oxone-promoted synthesis of 2,3-dihydroquinazoline-4(1H)-ones 11a–m.
Scheme 8
Scheme 8
Oxone-promoted synthesis of 1H-benzimidazoles 10.
Scheme 9
Scheme 9
Oxone/NaNO2-promoted oxidative radical cyclization of the propylamide 14.
Scheme 10
Scheme 10
Reaction mechanism for the Oxone/NaNO2-promoted oxidative annulation.
Scheme 11
Scheme 11
Oxone-mediated radical bicyclization of 1,6-enynes 17 and ketones 18.
Scheme 12
Scheme 12
Reaction mechanism for the Oxone-promoted bicyclization of 1,6-enynes 17.
Scheme 13
Scheme 13
Oxone/RSeSeR-promoted electrophilic cyclization of α,β-alkynyl hydrazones 20.
Scheme 14
Scheme 14
Reaction mechanism for the Oxone/RSeSeR-promoted electrophilic cyclization of α,β-alkynyl hydrazones 20.
Scheme 15
Scheme 15
Oxone-mediated multicomponent synthesis of substituted 4-organylselanylpyrazoles 22.
Scheme 16
Scheme 16
Oxone-promoted intramolecular dehydrogenative Povarov cyclization.
Scheme 17
Scheme 17
Synthetic application to construct complex structures, such as (A) the antibiotic Uncialamycin 26l and (B) the analogues of the cytotoxic alkaloid Luotonin A 26m and 26n.
Scheme 18
Scheme 18
ZnBr2/Oxone-mediated radical ipso-cyclization of alkynyl anilines 27.
Scheme 19
Scheme 19
Oxone/TBAB-mediated oxidative cyclization of N-aryl-2-arylbenzamides 29.
Scheme 20
Scheme 20
Oxone/TBAB-mediated synthesis of brominated products 31.
Scheme 21
Scheme 21
Oxone/TBAB-mediated synthesis of 3-bromo-1,2-dihydroquinoline derivatives 32.
Scheme 22
Scheme 22
Plausible mechanism for the radical 6-endo-trig cyclization of the substrate 33.
Scheme 23
Scheme 23
Oxone/TBAX-promoted tandem annulative radical halogenation of alkynyl imines.
Scheme 24
Scheme 24
Reaction mechanism for the Oxone/TBAX-promoted tandem annulative radical halogenation.
Scheme 25
Scheme 25
Oxone/Cu(NO3)2-promoted radical annulative nitration of 1,6-enynes 17.
Scheme 26
Scheme 26
Oxone/TBAX-promoted spirocyclization of p-methoxyl alkynyl-N-phenylimines 37.
Scheme 27
Scheme 27
Oxone/RSeSeR-promoted electrophilic cyclization of alkynylbenzaldoximes 39.
Scheme 28
Scheme 28
Oxone/RTeTeR-promoted electrophilic cyclization of alkynylbenzaldoximes 39.
Scheme 29
Scheme 29
Oxone/TBAB-promoted 5-exo-dig oxy-cyclization of 2-alkynylbenzamide 43. (A) Synthesis of isobenzofuran-1-imines 44. (B) Synthesis of isobenzofuran 45.
Scheme 30
Scheme 30
TBAB-catalyzed Oxone-mediated 6-endo-dig oxidative annulation of 2-alkynylbenzamide 43.
Scheme 31
Scheme 31
TBAB-catalyzed Oxone-mediated synthesis of isobenzofuran-1-imines 48.
Scheme 32
Scheme 32
Pd(II)-catalyzed Oxone-mediated oxidative annulation of 1,2-naphthofuroquinone 49 and diaryl alkynes 50.
Scheme 33
Scheme 33
Oxone/TBAB-promoted radical cyclization of 2-alkynylbenzoic acids 52.
Scheme 34
Scheme 34
Reaction mechanism of the Oxone/TBAB-promoted radical cyclization of 2-alkynylbenzoic acids 52.
Scheme 35
Scheme 35
Oxone/TBAB-promoted radical cyclization of 2-alkynylbenzoic acids 52.
Scheme 36
Scheme 36
Plausible mechanism of the Oxone/TBAB-promoted radical cyclization of 2-alkynylbenzoic acids 52.
Scheme 37
Scheme 37
Oxone/diselenide-promoted electrophilic cyclization of 2-alkynylaryl esters 56.
Scheme 38
Scheme 38
Oxone/ditelluride-promoted electrophilic cyclization of 2-alkynylaryl esters 56.
Figure 1
Figure 1
Structures of quaternary ammonium hypoiodite A and B.
Scheme 39
Scheme 39
Enantioselective oxidation of phenols 57a–f.
Scheme 40
Scheme 40
Enantioselective oxidation of 2-naphthols 59a–c.
Scheme 41
Scheme 41
Enantioselective Oxidation of 1-Naphthols 59d–f.
Scheme 42
Scheme 42
Oxone/dichalcogenide-promoted annulation of (Z)-1-butylselen-1-en-3-ynes 63.
Scheme 43
Scheme 43
Oxone/dichalcogenide-promoted annulation of (Z)-(1,4-diphenylbut-1-en-3-yn-1-yl)(propyl)sulfane 64a.
Scheme 44
Scheme 44
Oxone/dichalcogenide-promoted annulation of (Z)-butyl(1,4-diphenylbut-1-en-3-yn-1-yl)tellane 65a.
Scheme 45
Scheme 45
Reaction mechanism for the Oxone/dichalcogenide-promoted cyclization of chalcogenoenynes.
Scheme 46
Scheme 46
Oxone/dibutyl diselenide-promoted synthesis of thiophenes 67.
Scheme 47
Scheme 47
Oxone/dibutyl diselenide-promoted synthesis of thiophenes 68.
Scheme 48
Scheme 48
Oxone/dibutyl diselenide-promoted intramolecular cyclization of ortho-1,3-diynyl phenyl chalcogenide 69.
Scheme 49
Scheme 49
Oxone/diselenide-promoted electrophilic cyclization of 2-functionalized chalcogenoalkynes 71.
Scheme 50
Scheme 50
Oxone-mediated synthesis of 2-arylbenzoxazoles 73.
Scheme 51
Scheme 51
Oxone-mediated synthesis of 2-arylbenzothiazoles 74.
Scheme 52
Scheme 52
Reaction mechanism for the synthesis of 73 and 74.
Scheme 53
Scheme 53
Oxone/KBr-promoted bromo-cyclization of alkenyl carboxylic acids 77 (A) and N-allyl amides 78 (B).
Scheme 54
Scheme 54
Oxone/NBS-promoted synthesis of 2-aminobenzimidazoles 81 and 2-aminobenzoxazoles 82.
Scheme 55
Scheme 55
Ru-catalyzed Oxone-mediated intramolecular C−S coupling of N-arylthioureas 85.
Scheme 56
Scheme 56
Pd(II)-catalyzed Oxone-mediated enantioselective aza-Wacker type reaction.
Scheme 57
Scheme 57
Oxone-mediated synthesis of 3-arylisoxazole-4,5-dicarboxylates 89, through a one-pot process.
Scheme 58
Scheme 58
Oxone-mediated synthesis of 3-arylisoxazole-4,5-dicarboxylates 89, through a one-pot process.
Scheme 59
Scheme 59
Cu(II)-catalyzed Oxone-mediated one-pot synthesis of 3,5-diarylisoxazoles 92.
Scheme 60
Scheme 60
Oxone/dialkyl diselenide-promoted synthesis of 5H-selenopheno[3,2-c]isochromen-5-ones 94.
Scheme 61
Scheme 61
Competition between Se-cyclization and O-cyclization of the substrate 95d.
Scheme 62
Scheme 62
Plausible reaction mechanism for the formation of the products 94.
Scheme 63
Scheme 63
Oxone-mediated ipso-cyclization of N-arylpropiolamide 93 to access the spirocyclo derivatives 97.
Scheme 64
Scheme 64
Oxone-mediated ipso-cyclization of N-arylpropiolamide 96 to access the spirocyclo derivatives 98.
Scheme 65
Scheme 65
Oxone/diselenide-promoted ultrasound-assisted selective cyclization of unsaturated oximes 99.
Scheme 66
Scheme 66
Plausible reaction mechanism for the Oxone/diselenide-promoted ultrasound-assisted selective cyclization of unsaturated oximes 99. a: Radical mechanism. b: Ionic mechanism.
Scheme 67
Scheme 67
Oxone/diselenide-promoted synthesis of 2-aryl-(3-organocalcogenyl)thieno[2,3-b]pyridines 101.
Scheme 68
Scheme 68
Catalytic cyclization of alkenes 103 with aldoximes 104.
Scheme 69
Scheme 69
Mechanism proposed for the synthesis of isoxazoles 89n–s.
Scheme 70
Scheme 70
I+/Oxone catalyzed oxidative spiroetherification and spiroamination of phenols 105 and 106.
Scheme 71
Scheme 71
Oxone-mediated synthesis of isoxazolines 89t-ad.
Scheme 72
Scheme 72
Oxone-mediated synthesis of isoxazoles 92p–w.
Scheme 73
Scheme 73
Plausible mechanism for the catalytic cyclization of the substrate 104.
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