Recent Advances toward Electro- and Electrophotochemical 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-Catalyzed C—H/C—F Bonds Functionalization

doi:10.6023/cjoc202403010

Abstract

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancements in DDQ-catalyzed C—H bonds functionalization. Moreover, the challenging C—H functionalization of electron-deficient arenes has been achieved through the merger of electrochemical DDQ catalysis and photoirradiation. In addition, the synthetic utility of electrophotochemical DDQ catalysis was further demonstrated by the nucleophilic aromatic substitution (S_NAr) reaction of unactivated aryl fluorides. The recent developments in electro- and electrophotochemical DDQ-catalyzed C—H/C—F func- tionalizations with attention to their strategies and mechanistic insights are summarized. It is hoped that this not only deepens the understanding of this field, but also helps relevant researchers expand the application scope of DDQ catalysis.

Key words: 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), electrocatalysis, organic electrosynthesis, electrophotocatalysis, C—H functionalization, C—F functionalization

Cite this article

Yongmei Li, Liangbo Sun, Kun Xu, Chengchu Zeng. Recent Advances toward Electro- and Electrophotochemical 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-Catalyzed C—H/C—F Bonds Functionalization[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 668-676.

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Fig. & Tab. 11

Scheme 1. General catalytic modes for electro- and electrophotochemical DDQ catalysis

Scheme 2. Electrochemical DDQ-catalyzed intramolecular arene-arene coupling

Scheme 3. Electrochemical DDQ-catalyzed intramolecular C(sp2)—H esterification

Scheme 4. A plausible mechanism for the generation of lactone

Scheme 5. Electrophotochemical DDQ-catalyzed C(sp2)—H amination reactions

Scheme 6. Proposed mechanism for the generation of 9

Scheme 7. Electrophotochemical DDQ-catalyzed C(sp2)—H functionalization

Scheme 8. Electrochemical DDQ-catalyzed benzylic C—H amination

Scheme 9. Mechanism for the electrochemical benzylic C—H amination reaction

Scheme 10. Electrophotochemical DDQ-catalyzed C—F functionalization

Scheme 11. A plausible mechanism for the generation of 35

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基于2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)的电/光电催化在碳-氢和碳-氟键官能化中的应用进展