Research Progress in Benzene-Forming Cyclotrimerization Reactions

doi:10.6023/cjoc202407048

Abstract

Benzene-forming cyclotrimerization reactions are capable of constructing cyclic structures via continuous transformation of three identical functional groups, and have applications in various fields such as natural product synthesis, polymer chemistry, supramolecular chemistry, and material science. In this review, the recent advances in cyclotrimerization reactions forming a central benzene ring are systematically summarized according to the different reaction types of functional groups. In each typical example, the reaction conditions, mechanism, possible side reactions, and applications are discussed. A future perspective on benzene-forming cyclotrimerization reactions is also presented.

Key words: cyclotrimerization, C—C bond formation, organic synthesis, functional molecules, reaction mechanism

Cite this article

Cen Zhou, Xin Zhao, Xiao Zhang. Research Progress in Benzene-Forming Cyclotrimerization Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 42-55.

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Fig. & Tab. 22

Scheme 1. Reaction types of benzene-forming cyclotrimerization

Scheme 2. Typical mechanism of metal-catalyzed alkyne cyclotrimerization reaction

Scheme 3. Metal-free alkyne cyclotrimerization reactions and mechanism

Scheme 4. Regioselectivity in alkyne cyclotrimerization reactions

Figure 1. Synthesis of natural products or artificial structures via alkyne cyclotrimerization reactions

Scheme 5. Mechanism of carbonyl cyclotrimerization through consecutive aldol condensation

Scheme 6. Synthetic strategy of star-shaped molecules and dendrimers

Scheme 7. Construction of fused ring structures via carbonyl cyclotrimerization reactions

Scheme 8. Cyclotrimerization of carbonyl equivalents

Figure 2. Construction of hypercrosslinked porous materials via carbonyl cyclotrimerization reactions

Scheme 9. Synthesis of isotruxene from 1-indanone and 2-in- danone

Scheme 10. Cyclotrimerization of substituted alkenes/aryls

Scheme 11. Stereoselectivity in Stille-type cyclotrimerization reaction

Figure 3. Synthesis of host molecules via Stille-type cyclotrimerization reaction

Scheme 12. Stereoselectivity in Heck-type cyclotrimerization reaction

Figure 4. Synthesis of host molecules via Heck-type cyclotrimerization reaction

Scheme 13. Yamamoto-type cyclotrimerization reaction and mechanism

Figure 5. Synthesis of polyaromatic molecules via Yamamoto- type cyclotrimerization

Scheme 14. Synthesis of hexahydroxytriphenylene and its derivatives via oxidative cyclotrimerization reaction

Scheme 15. Synthesis of triindole and its derivatives via oxidative cyclotrimerization

Scheme 16. Synthesis of polyaromatic compounds via oxidative cyclotrimerization

Scheme 17. Organometallic oxidative cyclotrimerization reactions

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