3,3',5,5'-tetra-tert-butyldiphenoquinone (DPQ)

Product Manager：Nick Wilde

The commercially available organic oxidant 3,3',5,5'-tetra-tert-butyldiphenoquinone (DPQ) can be readily synthesized through the oxidation of the affordable o,o'-di-tert-butylphenol. DPQ functions as a two-electron acceptor, producing o,o'-di-tert-p-bisphenol as a readily separable byproduct. Additionally, near-quantitative yields can be achieved through reoxidation using oxygen in the presence of a base, making O2 the effective final oxidant in these reactions.(M. S. Kharasch, B. S. Joshi, J. Org. Chem. 1957, 22, 1439. DOI)

Compared to benzoquinone, one of the advantages lies in the non-nucleophilic nature of the reaction product of DPQ, allowing it to be utilized in electrophilic reactions without any interference.

Recent Literature

Cooperative carbene catalysis enables the selective oxidative acylation of alcohols with aldehydes, even when amino groups are present, through the use of an affordable and readily accessible organic oxidant. This proposed mechanism is supported by quantum chemical calculations.
S. De Sarkar, S. Grimme, A. Studer, J. Am. Chem. Soc., 2010, 132, 1190-1191.
https://doi.org/10.1021/ja910540j

An N-heterocyclic carbene catalyzes the oxidative esterification of various aldehydes with 3,3',5,5'-tetra-tert-butyldiphenoquinone to produce hexafluoroisopropylesters, which are valuable for in situ amide bond formation. This transition metal-free organocatalytic system also facilitates a gentle oxidative azidation process for aldehydes.
S. De Sarkar, A. Studer, Org. Lett., 2010, 12, 1992-1995.
https://doi.org/10.1021/ol1004643

An N-heterocyclic carbene catalyzes the oxidative esterification of various aldehydes with 3,3',5,5'-tetra-tert-butyldiphenoquinone to produce hexafluoroisopropylesters, which are valuable for in situ amide bond formation. This transition metal-free organocatalytic system also facilitates a gentle oxidative azidation process for aldehydes.
S. De Sarkar, A. Studer, Org. Lett., 2010, 12, 1992-1995.
https://doi.org/10.1021/ol1004643

An N-heterocyclic carbene serves as a catalyst for the oxidative esterification of aldehydes with 3,3',5,5'-tetra-tert-butyldiphenoquinone, yielding hexafluoroisopropylesters essential for creating amide bonds in situ. This organocatalytic system, which does not require transition metals, also enables a mild oxidative azidation reaction for aldehydes.
C. Zheng, Y. Liu, C. Ma, J. Org. Chem., 2017, 82, 6940-6945.
https://doi.org/10.1021/acs.joc.7b00457

A diverse array of functionalized Grignard compounds underwent coupling reactions facilitated by diphenoquinone as an electron acceptor. The oxidative dimerization of alkenylmagnesium reagents occurred while preserving the original stereochemistry intact.
A. Krasovskiy, A. Tishkov, V. del Amo, H. Mayr, P. Knochel, Angew. Chem. Int. Ed., 2006, 45, 5010-5014.
https://doi.org/10.1002/anie.200600772

An N-heterocyclic carbene-catalyzed reaction between enals and α-diketones allows for the highly diastereo- and enantioselective asymmetric synthesis of cyclopentenones. This method is compatible with substrates containing both aromatic and aliphatic groups.
Z. Chen, X. Kong, S. Niu, S. Yang, J. Liu, B. Chen, B. Luo, B. Luo, C. Zhou, C. Ding, X. Fang, Org. Lett., 2021, 23, 3403-3408.
https://doi.org/10.1021/acs.orglett.1c00870

An N-heterocyclic carbene catalyzes the oxidative LUMO activation of β-carbons in saturated carboxylic esters, enabling efficient asymmetric synthesis of lactams and lactones. This approach allows for the introduction of functional groups at typically unreactive β-sp3 carbons in saturated esters. The addition of HOBt enhances both the yields and enantioselectivities of the reactions.
B. Liu, W. Wang, R. Huang, J. Yan, J. Wu, W. Xue, S. Yang, Z. Jin, Y. R. Chi, Org. Lett., 2018, 20, 260-263.
https://doi.org/10.1021/acs.orglett.7b03650

An N-heterocyclic carbene catalyzes a [3+3] annulation reaction between β-ketone esters and enynals, leading to pentasubstituted 4H-pyran derivatives via regioselective activation of the ynal. This process results in the synthesis of a range of 4H-pyran derivatives with various substituents in good yields.
X. Peng, Y. Wang, Y. Huang, S. Zhang, Z. Jin, S.-C. Ren, Synlett, 2024, 35, 1185-1189.
https://doi.org/10.1055/a-2253-4365

Under mild conditions, an intramolecular cyclization reaction catalyzed by an N-heterocyclic carbene (NHC) of aldimines derived from 2-amino phenols and aromatic aldehydes yields 2-arylbenzoxazoles in good amounts. This reaction is compatible with a wide variety of functional groups.
A. Patra, A. James, T. K. Das, A. T. Biju, J. Org. Chem., 2018, 83, 14820-14826.
https://doi.org/10.1021/acs.joc.8b02598

The [4+3] annulation of salicylaldehydes with aziridines, cocatalyzed by an N-heterocyclic carbene and copper, results in the formation of 1,4-benzoxazepinones in good yields and with exclusive regioselectivity.
Y.-F. Han, Z.-H. Gao, C.-L. Zhang, S. Ye, Org. Lett., 2020, 22, 8396-8400.
https://doi.org/10.1021/acs.orglett.0c03026

Quoted from: 

https://www.organic-chemistry.org/chemicals/oxidations/dpq-3,3',5,5'-tetra-tert-butyldiphenoquinone.shtm

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