三聚苯环化反应的研究进展

doi:10.6023/cjoc202407048

摘要/Abstract

三聚苯环化反应是通过同种官能团的连续转化形成苯环的一类反应, 在天然产物合成、高分子化学、超分子化学、材料科学等诸多领域被广泛应用. 按照官能团转化的种类, 对近年来通过特定官能团三聚转化形成苯环的反应进行了系统性总结归纳, 对每类反应的条件、机理、可能存在的副反应、主要应用实例等内容进行了介绍, 并对该领域未来的发展方向进行了展望.

关键词: 三聚环化, 碳-碳键构筑, 有机合成, 功能分子, 反应机理

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

引用此文

周岑, 赵新, 张霄. 三聚苯环化反应的研究进展[J]. 有机化学, 2025, 45(1): 42-55.

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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图/表 22

图式1. 三聚苯环化反应的种类

Scheme 1. Reaction types of benzene-forming cyclotrimerization

图式2. 金属催化的炔基环化三聚反应的典型机理

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

图式3. 无金属催化的炔基三聚环化反应及其机理

Scheme 3. Metal-free alkyne cyclotrimerization reactions and mechanism

图式4. 炔基三聚环化反应中的区域选择性调控

Scheme 4. Regioselectivity in alkyne cyclotrimerization reactions

图1. 通过炔基三聚环化反应构筑的天然产物或人工结构

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

图式5. 通过羰基的连续羟醛缩合反应实现三聚的机理

Scheme 5. Mechanism of carbonyl cyclotrimerization through consecutive aldol condensation

图式6. 星状分子和树枝状大分子的合成策略

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

图式7. 通过环内羰基的三聚反应构筑的并环结构

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

图式8. 羰基等效体的三聚反应

Scheme 8. Cyclotrimerization of carbonyl equivalents

图2. 通过羰基三聚反应构筑的交联多孔材料

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

图式9. 通过1-茚酮与2-茚酮的反应合成异三聚茚

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

图式10. 取代烯基或芳基的三聚反应

Scheme 10. Cyclotrimerization of substituted alkenes/aryls

图式11. Stille类烯基三聚反应的立体选择性问题

Scheme 11. Stereoselectivity in Stille-type cyclotrimerization reaction

图3. 通过Stille类三聚反应合成的主体分子

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

图式12. Heck类烯基三聚反应中syn产物的形成机理

Scheme 12. Stereoselectivity in Heck-type cyclotrimerization reaction

图4. 通过Heck类烯基三聚反应合成的主体分子

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

图式13. Yamamoto类烯基三聚反应及其机理

Scheme 13. Yamamoto-type cyclotrimerization reaction and mechanism

图5. 通过Yamamoto类三聚反应合成的稠环分子

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

图式14. 通过氧化偶联三聚反应合成六羟基苯并菲及其衍生物

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

图式15. 通过氧化偶联三聚反应合成三聚吲哚及其衍生物

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

图式16. 通过氧化偶联三聚反应合成稠环芳香化合物

Scheme 16. Synthesis of polyaromatic compounds via oxidative cyclotrimerization

图式17. 通过金属有机试剂实现的氧化偶联三聚反应

Scheme 17. Organometallic oxidative cyclotrimerization reactions

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