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Review
. 2021 Sep 8;11(47):29826-29858.
doi: 10.1039/d1ra04575j. eCollection 2021 Sep 1.

DDQ as a versatile and easily recyclable oxidant: a systematic review

Meshari A Alsharif  1 , Qandeel Alam Raja  2 , Nida Abdul Majeed  2 , Rabab S Jassas  3 , Abdulrahman A Alsimaree  4 , Amina Sadiq  5 , Nafeesa Naeem  2 , Ehsan Ullah Mughal  2 , Reem I Alsantali  6 , Ziad Moussa  7 , Saleh A Ahmed  1   8   9
Affiliations
Review

DDQ as a versatile and easily recyclable oxidant: a systematic review

Meshari A Alsharif et al. RSC Adv. .

Abstract

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is the most widely used quinone with a high reduction potential, and it commonly mediates hydride transfer reactions and shows three accessible oxidation states: quinone (oxidized), semiquinone (one-electron-reduced), and hydroquinone (two-electron-reduced). DDQ has found broad utility as a stoichiometric oxidant in the functionalization of activated C-H bonds and the dehydrogenation of saturated C-C, C-O, and C-N bonds. The cost and toxicity of DDQ triggered recent efforts to develop methods that employ catalytic quantities of DDQ in combination with alternative stoichiometric oxidants. The aerobic catalytic approach was established for the selective oxidation of non-sterically hindered electron-rich benzyl methyl ethers and benzylic alcohols, and effectively extended to the oxidative deprotection of p-methoxybenzyl ethers to generate the alcohols in high selectivity. A combination of DDQ and protic acid is known to oxidize several aromatic donors to the corresponding cation radicals. The excited-state DDQ converts benzyls, heteroarenes, fluoroarenes, benzene, and olefins into their radical cation forms as well as chloride and other anions into their respective radicals. These reactive intermediates have been employed for the generation of C-C and C-X (N, O, or Cl) bonds in the synthesis of valuable natural products and organic compounds. To the best of our knowledge, however, there is still no review article exclusively describing the applications of DDQ in organic synthesis. Therefore, in the present review, we provide an overview of DDQ-induced organic transformations with their scope, limitations and the proposed reaction mechanisms.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. DDQ as an oxidant.
Scheme 2
Scheme 2. Synthesis of DDQ.
Scheme 3
Scheme 3. Benzylic alcohol oxidation by DDQ.
Scheme 4
Scheme 4. DDQ-induced oxidation of naphthol like compound 3.
Scheme 5
Scheme 5. Oxidation of 1,2-diols by DDQ.
Scheme 6
Scheme 6. DDQ initiated oxidation of alcohols.
Scheme 7
Scheme 7. Selective benzylic oxidation of β-O-4 model compound 15.
Scheme 8
Scheme 8. Selective benzylic alcohol oxidation by DDQ.
Scheme 9
Scheme 9. Oxidation of benzylic alcohols.
Scheme 10
Scheme 10. Oxidation of ethers to enones by DDQ.
Scheme 11
Scheme 11. Oxidation of allylic ethers by DDQ.
Scheme 12
Scheme 12. DDQ mediated selective benzylic oxidation.
Scheme 13
Scheme 13. Oxidation-initiated cyclization of pentadienyl ethers by DDQ.
Scheme 14
Scheme 14. Construction of 8-azacyclooctanes by DDQ mediated reactions.
Scheme 15
Scheme 15. A carbon–carbon bond formation by DDQ.
Scheme 16
Scheme 16. DDQ-mediated oxidative cyclization via Scholl reaction.
Scheme 17
Scheme 17. Skeletal rearrangement under Scholl's reaction conditions by DDQ.
Scheme 18
Scheme 18. Synthesis of rubicene derivatives under Scholl's reaction conditions.
Scheme 19
Scheme 19. DDQ/FeCl3-controlled sequential oxidative C–C bond formation.
Scheme 20
Scheme 20. Removal of p-methoxybenzyl protection by DDQ.
Scheme 21
Scheme 21. Deprotection of PMB-protected primary hydroxyl group by DDQ.
Scheme 22
Scheme 22. Cleavage of DMPM protecting group for hydroxy functionality by DDQ oxidation.
Scheme 23
Scheme 23. Deprotection of PMB for hydroxy functionality by DDQ.
Scheme 24
Scheme 24. DDQ-mediated oxidative removal of acetal.
Scheme 25
Scheme 25. Oxidative deprotection of diphenyl methylamines by DDQ.
Scheme 26
Scheme 26. Deprotection of benzyl phenyl by DDQ.
Scheme 27
Scheme 27. DDQ-promoted synthesis of 2-arylbenzoxazoles.
Scheme 28
Scheme 28. Deprotection of benzyl ethers using DDQ.
Scheme 29
Scheme 29. Deprotection of hydroxyisochromans by DDQ.
Scheme 30
Scheme 30. Deprotection of benzyl-type ethers by DDQ/tert-butyl nitrite mixture.
Scheme 31
Scheme 31. N-Allylic amine deprotection using DDQ.
Scheme 32
Scheme 32. p-Methoxybenzyl ether deprotection by DDQ.
Scheme 33
Scheme 33. DDQ controlled regiospecific protection and deprotection of primary alcohol.
Scheme 34
Scheme 34. Oxidation of sterically hindered phenols by DDQ.
Scheme 35
Scheme 35. Oxidation of 4-hydroxytriphenylethane.
Scheme 36
Scheme 36. Oxidative cyclization of a substituted phenol by DDQ.
Scheme 37
Scheme 37. Oxidation of alkyl-enol ethers by DDQ.
Scheme 38
Scheme 38. Synthesis of various steroids structures via DDQ-initiated oxidation.
Scheme 39
Scheme 39. Dehydrogenation of ketosteroids by DDQ.
Scheme 40
Scheme 40. Oxidation of hydroxysteroids by DDQ.
Scheme 41
Scheme 41. Dehydrogenation of acetoxy ketones.
Scheme 42
Scheme 42. Aromatization induced by DDQ.
Fig. 1
Fig. 1. Aromatization using quinone-based oxidants.
Fig. 2
Fig. 2. Hydrocarbons prepared by the dehydrogenation of cholesterol.
Fig. 3
Fig. 3. Aromatization promoted by DDQ.
Scheme 43
Scheme 43. Oxidative coupling by DDQ.
Scheme 44
Scheme 44. Synthesis of Efavirenz by DDQ-mediated oxidation.
Scheme 45
Scheme 45. Oxidative cyclotrimerization of 1,2-dimethoxybenzene induced by DDQ.
Scheme 46
Scheme 46. Dehydrogenation of 7-hydroxyflavanone (128a) and 7-methoxyflavanone (128b).
Scheme 47
Scheme 47. Dehydrogenation of flavanones with DDQ.
Scheme 48
Scheme 48. Dehydrogenation of 1-thioflavanone and 3-bromo analog by DDQ.
Scheme 49
Scheme 49. Conversion of catechin to flavanol analog by DDQ.
Scheme 50
Scheme 50. Synthesis of 5,2′-dihydroxy-7-methoxyflavone and flavanone.
Scheme 51
Scheme 51. Dehydrogenation of 1,4-cyclohexadiene by DDQ.
Scheme 52
Scheme 52. Dehydrogenation of dihydroarenes by DDQ.
Scheme 53
Scheme 53. DDQ controlled oxidation-dehydrogenation of dihydrobenzopyrans.
Scheme 54
Scheme 54. Secondary amine dehydrogenation by DDQ.
Scheme 55
Scheme 55. DDQ-induced dehydrogenation of saturated heterocycles.
Fig. 4
Fig. 4. Possible mechanistic pathways for the C–H abstraction from Scholl's precursors by DDQ.
Scheme 56
Scheme 56. Synthesis of soluble HBCs from hexaarylbenzene precursors.
Scheme 57
Scheme 57. Synthesis of a series of HBC derivatives containing EWGs via DDQ.
Scheme 58
Scheme 58. Synthesis of hexabenzoperylene via DDQ.
Scheme 59
Scheme 59. DDQ-induced synthesis of grossly warped graphene molecules.
Scheme 60
Scheme 60. Synthesis of biphenylene-based PAH by DDQ.
Scheme 61
Scheme 61. Synthesis of PAHs by DDQ.
Scheme 62
Scheme 62. Graphene syntheses with an embedded 7-membered ring through cyclodehydrogenation.
Scheme 63
Scheme 63. DDQ promoted oxidative cycloheptatriene ring formation around the TBTQ core.
Scheme 64
Scheme 64. DDQ-mediated Scholl-type oxidative cycloheptatriene formation; a fourfold bridging of the fenestrindanes core with electron-rich aryl units.
Scheme 65
Scheme 65. Synthetic route to the synthesis of hexapyrrolohexaazacoronenes by DDQ.
Scheme 66
Scheme 66. DDQ–TfOH-promoted Scholl macrocyclization for porous nanographene syntheses.
Scheme 67
Scheme 67. Synthesis of O-annulated PAHs by DDQ.
Scheme 68
Scheme 68. Oxidative aromatic coupling by DDQ.
Scheme 69
Scheme 69. Synthesis of the aromatic saddle-shaped nanographenes by DDQ/TfOH system.
Scheme 70
Scheme 70. Synthesis of the π-extended nanographene from the aryloxy-substituted TBTQ via DDQ.
Scheme 71
Scheme 71. Amination of aromatic ring via DDQ under visible light irradiation.
Scheme 72
Scheme 72. Radical trifluoromethylation of six-membered aromatics.
Scheme 73
Scheme 73. DDQ-photocatalyzed direct C2–H amination of thiophene under visible-light irradiation.
Scheme 74
Scheme 74. DDQ-catalyzed transformation of varyingly substituted 1,3-butadienes under visible-light-irradiation.
Scheme 75
Scheme 75. DDQ-assisted direct C–F amination of chlorofluoroarenes by pyrazoles under visible-light irradiation.
Scheme 76
Scheme 76. DDQ-assisted oxidative debenzylation of benzyl ethers under visible-light irradiation.
None
Ehsan Ullah Mughal
None
Saleh A. Ahmed
See this image and copyright information in PMC

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