Artificial sugar saccharin and its derivatives: role as a catalyst

Abstract

The primary objective of this review was to demonstrate the significance of artificial sugar saccharin and its derivatives as catalysts for a wide variety of organic transformations. The application of saccharin and its derivatives represents a greener and superior catalytic approach for reactions. In particular, we were interested in bringing together the literature pertaining to these saccharin derivatives from a catalysis perspective. The present review reports synthesis of saccharin and its derivatives such as saccharin-N-sulfonic acid, sodium saccharin, N-halo saccharin, saccharin lithium-bromide, N-formyl saccharin, N-acyl saccharin, N-nitrosaccharin, N-SCF₃ saccharin, N-fluorosultam, N-phenylselenosaccharin, N-thiocyanatosaccharin palladium saccharin, DMAP-saccharin, and [Bmim]Sac. This catalytic application of saccharin and its derivatives includes reactions such as the Biginelli reaction, Paal-Knorr pyrrole synthesis, azo-coupling reaction, halogenations, domino Knoevenagel, Michael, deoximation reaction, catalytic condensation, functional group protection and oxidation etc. Also, these saccharin derivatives act as a source of CO, NH₂, SCN, SCF₃ and nitro groups. We reported all the available data on saccharin and its derivatives acting as a catalyst from 1957 to date.

Scheme 1. Quinoxalines and pyrido[2,3-b]pyrazines synthesis.

Scheme 2. Paal–Knorr pyrroles synthesis.

Scheme 3. Synthesis of dihydro-2-oxypyrrole.

Scheme 4. Synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-dione.

Scheme 5. Synthesis of 3,4-dihydropyrimidin-2-(1H)-one.

Scheme 6. Synthesis of pyrano[2,3-d]pyrimidinone scaffolds.

Scheme 7. Synthesis of dihydropyrano[2,3-c]pyrazole.

Scheme 8. Synthesis of tetrahydrobenzo[b]pyran.

Scheme 9. Synthesis of 4-amidocinnoline derivatives.

Scheme 10. Proposed mechanism for the synthesis of 4-amidocinnolines derivatives.

Scheme 11. Synthesis of 1,2,3-benzotriazine-4-(3H)-ones using saccharin as catalyst.

Scheme 12. Synthesis of 4-hydroxy-3-[(E)-aryldiazenyl]-benzaldehyde derivatives via stable arene diazonium saccharinates.

Scheme 13. Mechanism of diazotization process.

Scheme 14. Synthesis of saccharin-N-sulfonic acid (SaSA).

Scheme 15. Trimethylsilyation of alcohol is carried out in the presence of SaSA with HDMS.

Scheme 16. Conversion of aldehyde to their corresponding 1,1-diacetate with acetic anhydride by using SaSA as catalyst.

Scheme 17. Mechanism for the synthesis of 1,1-diacetate.

Scheme 18. Acetylation of alcohols, phenols and amines in presence of SaSA as catalyst.

Scheme 19. Formation of N-Boc protected amines.

Scheme 20. Formation of tert-butyl ether by using SaSA as a catalyst.

Scheme 21. The condensation of 2-naphthol with the arylaldehyde and amides.

Scheme 22. The mechanism for the formation of 1-amidoalkyl-2-naphthol.

Scheme 23. Synthesis of N,N′-alkylidene bisamides.

Scheme 24. The mechanism proposed for the synthesis of N,N′-alkylidiene bisamide.

Scheme 25. Synthesis of 1,8-dioxo-octahydroxanthenes and 14-aryl-14H-dibenzoxanthene derivatives.

Scheme 26. Synthesis of N-bromosaccharin.

Scheme 27. Bromination of phenols and anilines using N-bromosaccharin.

Scheme 28. Mechanism for the synthesis of bromo aniline and phenol using NBSac–H₃PW₁₂O₄₀.

Scheme 29. Bromination of phenol with NBSac over ZSM-5 zeolite.

Scheme 30. Monobromination of 1,3-diones using N-bromosaccharin/Mg(ClO₄).

Scheme 31. Halogenation of aromatic ring.

Scheme 32. Cohalogenation of alkenes.

Scheme 33. Halogenation of α,β-unsaturated ketones, nitriles, esters and acids in presence of N-iodo and N-bromosaccharin.

Scheme 34. Conversion of oximes to corresponding ketones or aldehydes in presence of N-bromosaccharin.

Scheme 35. Deoximation of oxime.

Scheme 36. Oxidation of thiols to the disulfides.

Scheme 37. Possible mechanisms for the oxidation of thiols to disulfides.

Scheme 38. Possible mechanisms for the oxidation of thiols to disulfides.

Scheme 39. Oxidation of alcohol to corresponding carbonyl compound by NBSac.

Scheme 40. Synthesis of 1,3-oxathiolane.

Scheme 41. Bromoamidation and bromoether adduct formation.

Scheme 42. Visible light photolytic imidation with N-bromosaccharin.

Scheme 43. (a) Conversion of trimethylsilyl ether and (b) conversion of tetrahydropyranyl ethers in presence of N-iodo and N-bromo saccharin in presence of Ph₃P.

Scheme 44. Synthesis of N-iodosaccharin.

Scheme 45. Iodination of aromatic ring.

Scheme 46. Iodination of substituted ring.

Scheme 47. Iodination of 1,3-diones and enol acetate.

Scheme 48. Synthesis of 1,3-oxazine.

Scheme 49. Synthesis of [Bmim]Sac.

Scheme 50. Synthesis of indole-3-dihydrocoumarin.

Scheme 51. Mechanism for synthesis of indole-3-dihydrocoumarin.

Scheme 52. 3,4-Dihydropyrano[c]chromenes, 4,5-dihydropyrano[4,3-b]pyran, and tetrahydrobenzo[b]pyrans scaffolds.

Scheme 53. Mechanism proposed for the dual activation of IL.

Scheme 54. Domino Knoevenagel–Michael reaction of substituted aldehydes catalyzed by [Bmim]Sac.

Scheme 55. Mechanism via dual of hydrogen bonding of saccharinate anion and dual activation of [Bmim]Sac.

Scheme 56. Synthesis of Bignelli and Hantzach product using [Bmim]Sac.

Scheme 57. Synthesis of ferrocenyl thiopropanones.

Scheme 58. Role of [Bmim][Sac] in the thia Michael addition of ferrocenyl enone.

Scheme 59. Synthesis of isocyanurates.

Scheme 60. Synthesis of 4-arylidene-3-methylisoxazol-5(4H)-ones.

Scheme 61. Mechanism followed for the synthesis of 4-arylidene-3-methylisoxazol-5(4H)-one.

Scheme 62. Synthesis of dihydropyrano[2,3-g]chromenes.

Scheme 63. Mechanism purposed for synthesis of dihydropyrano[2,3-g]chromenes.

Scheme 64. Synthesis of N-formylsaccharin.

Scheme 65. Formylation of primary amines.

Scheme 66. N-Formylation of benzyl amines.

Scheme 67. Synthesis of aldehydes from aryl halides.

Scheme 68. Flourocarbonylation of aryl halides.

Scheme 69. Phenylcarbonylation to synthesize aryl esters.

Scheme 70. Direct synthesis of aromatic azides from aryl bromides and NaN₃.

Scheme 71. Methoxycarbonylation of styrene.

Scheme 72. Thiocarbonylation of styrene with thiol.

Scheme 73. A palladium-catalyzed carbonylative and reductive cyclization.

Scheme 74. Synthesis of N-acyl and N-alkyl saccharin derivatives.

Scheme 75. Pd-catalyzed acylative Suzuki coupling of amides.

Scheme 76. Pd-catalyzed Suzuki–Miyaura coupling of N-acylsaccharin.

Scheme 77. Diamination of amide.

Scheme 78. Decarbonylative Heck reaction of amides via C–N activation.

Scheme 79. (a) trans-Benzoylation Sonogashira cross-coupling in GIL using N-benzoylsaccharin, (b) trans-benzoylation Suzuki cross-coupling using N-benzoylsaccharin, and (c) decarbonylative Heck coupling in GIL using N-benzoylsaccharin.

Scheme 80. (a) Synthesis of N-nitro saccharin. (b). Nitration of arenes.

Scheme 81. (a) Synthesis of N-trifluoromethylthiosaccharin (b) trifluorothiolating reagent for various nucleophile.

Scheme 82. Synthesis of trifluoromethylthiolated lactam/lactone.

Scheme 83. Proposed mechanism.

Scheme 84. Enantioselective trifluoromethythiolation lactonization of alkenes.

Scheme 85. Activation of triglycosides by trifluoromethylthiosaccharin.

Scheme 86. Synthesis of N-flourosultam from saccharin.

Scheme 87. Fluorination of carbonyl compound.

Scheme 88. (a) Synthesis of N-phenylselenosaccharin (b) phenylselenylation of electron rich molecules.

Scheme 89. (a) Synthesis of N-thiocyanatosaccharin (b) reaction of N-thiocyanatosaccharin with different nucleophile.

Scheme 90. Synthesis of N-tosylimines directly from alcohols.

Scheme 91. Mechanism followed for the formation of N-sulfonylimines.

Scheme 92. Synthesis of palladium saccharin.

Scheme 93. Aminooxygenation catalyzed by palladium catalyzed of allyl ether or ester.

Scheme 94. Palladium-catalyzed diamination of terminal alkenes with Pd(NCMe)₂(Sacch)₂.

Scheme 95. Mechanism of palladium-catalyzed difunctionalization reaction with saccharin.

Scheme 96. Palladium catalyzed diamination of alkene.

Scheme 97. DMAP–Saccharin catalyzed acylation of 1-cyclohexanol.

Scheme 98. Acylation reaction of alcohol with acid anhydride catalyzed by pyridinium saccharin salt.

Scheme 99. Mechanism of DMAP catalyzed acylation reaction based on synthon connectivity as the resting state with O(sac)⋯HeN(py)/O(sac)–H. N(py) for propagation.

Scheme 100. Proposed ring-opening polymerization mechanisms of cyclic esters using pyridinium saccharinate as the co-catalyst.

Scheme 101. (a) Synthesis of tetrazole-amino-saccharin (b) oxidation of benzyl alcohol under microwave condition in presence of tetrazole-amino-saccharin.

Fig. 1. Structure of 1- and 2-methyltetrazole-saccharinate.

Scheme 102. (a) Synthesis of (tetrazole-saccharin) nickel complex (b) hydrosilative reductive of aldehydes in presence of nickel complex.

Scheme 103. Conversion of alcohols to respective ketones.

Scheme 104. Synthesis of saccharin based μ-oxo-bridged imidoiodane.

Scheme 105. Synthesis of α-aminated carbonyl compound using saccharin based μ-oxo-bridged imidoiodane.

Scheme 106. Direct oxidative amidation of aldehyde or methyl arenes.

Scheme 107. Catalytic cycle of oxidative amination of aldehyde.

Scheme 108. Regioselective amination of unsymmetrical 3,5-substituted pyridine N-oxides.

Scheme 109. Synthesis of N,N′-carbonyldisaccharin.

Scheme 110. Synthesis of (a) peptides, (b) esters, and (c) amides by the use of condensing reagent.

Kamalpreet Kaur

Suman Srivastava