Research Progress on C2—C3 Bond Cleavage of Indole and Its Derivatives

doi:10.6023/cjoccjoc202203014

Abstract

Indole building blocks widely exist in many important natural products and drug molecules, and are known as star molecules in bioactive drugs. In view of the outstanding value of indole-based molecules in the field of clinical treatment and drug development, the efficient construction, synthetic transformation and late-stage modification of indole molecules has been an enduring research hotspot in the field of organic synthesis. In recent years, the C2—C3 bond cleavage and reconstruction of indoles have played an important role in the construction of complex molecules and the synthesis of drug molecules, attracting extensive research interests from chemists. This paper systematically summarizes the research progress of C2—C3 bond cleavage/reconstruction reactions of indole and its derivatives in recent years with particular emphasis on reaction strategies, substrate scope and mechanisms.

Key words: indole, indole derivatives, cleavage of C2—C3 bond, reaction mechanism

Cite this article

Zexin Huang, Yuqiang Yin, Fengcheng Jia, Anxin Wu. Research Progress on C2—C3 Bond Cleavage of Indole and Its Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2028-2044.

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Fig. & Tab. 33

Scheme 1. Palladium-catalyzed ring-expansion reaction of indoles with alkynes

Scheme 2. Copper-catalyzed oxidative ring-expansion reaction of 3-dienylindoles

Scheme 3. Ring-expansion reaction of indoles with 2-butynedioates

Scheme 4. Oxidative ring-expanding reaction of 2-arylindoles for synthesis of 2-arylbenzoxazinones

Scheme 5. Copper-catalyzed aerobic oxidative ring-expanding reaction of 2?arylindoles with amines

Scheme 6. Oxidative recyclization of 1H?indoles for synthesis of 2?indolylbenzoxazinones via cleavage of the C2-C3 bond

Scheme 7. Copper-catalyzed construction of eight-membered rings via oxidative ring-expanding reaction of indoles with amidines

Scheme 8. Visible-light-induced oxidative ring expansion of indoles with amidines

Scheme 9. Copper-catalyzed oxidative ring expansion of indoles and enaminone analogues

Scheme 10. Visible light-induced aerobic oxidative ring expansion of indole derivatives

Scheme 11. Copper-catalyzed diazidation and ring expansion cascade of 2-arylindoles with TMSN3

Scheme 12. Synthesis of 2?aminobenzonitriles through tert-butylnitrite (TBN)-mediated nitrosation reaction and sequential Iron(III)-catalyzed C—C bond cleavage of 2?arylindoles

Scheme 13. Selective oxidative cleavage of 3?methylindoles with primary amines a?ording quinazolinones

Scheme 14. Oxidative cleavage of indoles mediated by H2O2 in polar solvents

Scheme 15. Aryne insertion into C2—C3 bond of indolin-2- ones

Scheme 16. Base-promoted ring expansion reaction of indolin- 2-ones with alkynyl ketones

Scheme 17. Oxidative fragmentations and skeletal rearrangements of oxindole derivatives

Scheme 18. 3,3-Diazidooxindole-involved C—C bond cleavage/reorganization

Scheme 19. Oxidative fragmentation and skeletal rearrangement of peroxyoxindole

Scheme 20. Oxygen-dominated C2—C3 bond cleavage of indolin-2-ones

Scheme 21. Oxygen-dominated C2—C3 bond cleavage of indolin-2-ones

Scheme 22. Ring expansion reaction of spirocyclic indolones involving 1,5-sigmatropic rearrangement

Scheme 23. TBHP-mediated oxidative ring expansion of isatins and amidine hydrochlorides

Scheme 24. TBHP-promoted cascade oxidative cyclization and interrupted dimroth rearrangement

Scheme 25. TBHP-mediated oxidative ring expansion of isatin to construct quinolones

Scheme 26. O2-promoted oxidative ring expansion of isatins and o-phenylene diamines

Scheme 27. TBHP/TFA promoted oxidative cyclization of isatins with 1,2,3,4-tetrahydroisoquinolines

Scheme 28. Copper-catalyzed decarbonylation coupling of N-pyridyl-substituted isatins

Scheme 29. Copper-catalyzed decarboxylative coupling reactions of isatins with arylglyoxylic acids

Scheme 30. Iron-catalyzed domino reaction of isatins and trifluoroacetimidoyl chlorides

Scheme 31. Copper-catalyzed decarbonylation coupling of N-aryl substituted isatins

Scheme 32. Et3N-promoted three-component tandem cyclization related to isatins

Scheme 33. p-TSA-promoted three-component tandem cyclization related to isatins

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