Recent Advances in Electrochemical-Promoted Unactivated C(sp3)—H Functionalization

doi:10.6023/cjoc202309024

Abstract

Organic electrosynthesis replaces traditional chemical oxidants or reductants with traceless electrons, which has the advantages of sustainability and easy to scale up. The functionalization of unactivated C(sp³)—H bond can directly introduce the target functional group into the molecules, avoiding pre-functionalization and possessing both atomic and step economies. With the development of organic electrosynthesis, electrochemical-promoted functionalization of unactivated C(sp³)—H bond has become one of the hotspots in organic synthesis. The functional groups are classified according to the types of functional groups, and the recent achievements related to the functionalization of unactivated C(sp³)—H bond are summarized, with emphasis on analyzing reaction advantages, substrate scope, and reaction mechanism. Finally, the current challenges and future development are briefly discussed.

Key words: organic electrosynthesis, unactivated C(sp³)—H bond, functionalization

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Ruilin Gao, Lirong Wen, Weisi Guo. Recent Advances in Electrochemical-Promoted Unactivated C(sp³)—H Functionalization[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 892-902.

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Fig. & Tab. 15

Figure 1. BDE of C(sp3)—H bond

Scheme 1. Reaction activation mode

Scheme 2. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond mediated by quinuclidine

Scheme 3. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond mediated by N-ammonium ylide

Scheme 4. Electrochemical-promoted hydroxylation of unactivated C(sp3)—H bond

Scheme 5. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond catalyzed by palladium

Scheme 6. Photoelectrocatalyzed oxidation of unactivated C(sp3)—H bond

Scheme 7. Photoelectrocatalyzed azidation of unactivated C(sp3)—H bond

Scheme 8. Electrochemical-promoted azidation of unactivated C(sp3)—H bond catalyzed by manganese

Scheme 9. Electrochemical-promoted amination of unactivated C(sp3)—H bond

Scheme 10. Photoelectrocatalyzed for heteroaromatization of unactivated C(sp3)—H bond

Scheme 11. Electrochemical-promoted heteroaromatization of unactivated C(sp3)—H bond

Scheme 12. Photoelectrocatalyzed cross coupling of unactivated C(sp3)—H bond with benzothiazoles

Scheme 13. Electrochemical-promoted fluorination of unactivated C(sp3)—H bond

Scheme 14. Electrochemical-promoted alkenylation and acylation of unactivated C(sp3)—H bond

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电化学促进未活化C(sp³)—H官能团化研究进展

Recent Advances in Electrochemical-Promoted Unactivated C(sp³)—H Functionalization

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Fig. & Tab. 15

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