机械手性轮烷研究进展

doi:10.6023/cjoc202504033

摘要/Abstract

机械手性轮烷作为机械互锁分子的重要分支, 凭借机械键诱导的独特立体化学特性, 在分子机器与不对称催化等领域展现出广阔应用前景. 根据组件的对称性特征, 轮烷的机械手性主要分为机械面手性、机械轴手性与机械点手性三类. 此文基于非手性组件的对称面分析, 组合各种类型的大环和轴体, 阐述了这三类机械手性的特征. 当前, 机械手性轮烷的制备主要是基于手性池和手性辅基的非对映选择性合成策略, 基于手性催化剂的对映选择性催化合成机械面手性和机械点手性轮烷也有少量报道. 按轮烷的机械手性分类, 从合成方法上对该领域现状和未来发展进行了总结与展望, 并简要介绍了机械手性轮烷的应用.

关键词: 轮烷, 机械面手性, 机械轴手性, 对称面, 不对称合成

Mechanically chiral rotaxanes, as a critical subclass of mechanically interlocked molecules (MIMs), demonstrate broad application prospects in molecular machines and asymmetric catalysis due to their unique stereochemical properties induced by mechanical bonds. Based on the symmetry feature of their components, mechanical chirality of rotaxanes is classified into three categories: mechanically planar chirality, mechanically axial chirality, and mechanical point-chirality. The stereochemical features of these three types are elucidated by analyzing the symmetry planes of each achiral macrocycle and axle, and then combining these two components. Currently, the preparation of mechanically chiral rotaxanes mainly relies on diastereoselective strategies employing chiral pools or chiral auxiliaries. A limited number of catalytic enantioselective synthesis of mechanically planar chiral and mechanically point-chiral rotaxanes have been reported. The current status and future directions in the field are systematically summarized, categorized by the types of rotaxane chirality and their corresponding synthetic strategies. Application of mechanically chiral rotaxanes is also briefly introduced.

Key words: rotaxane, mechanically planar chirality, mechanically axial chirality, symmetry plane, asymmetric synthesis

引用此文

朱瑞卿, 朱婷, 王超, 宗利利. 机械手性轮烷研究进展[J]. 有机化学, 2025, 45(12): 4239-4256.

Ruiqing Zhu, Ting Zhu, Chao Wang, Lili Zong. Research Progress in Mechanically Chiral Rotaxanes[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4239-4256.

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图/表 30

图1. 点手性、轴手性、面手性和螺旋手性的分子实例

Figure 1. Examples of covalent chiral molecules with point, axial, planar and helical chirality

图2. 共价手性轴体或大环构成的手性轮烷实例

Figure 2. Examples of chiral rotaxanes composed of covalent chiral axle or macrocycle

图3. 轮烷非手性组件的示意图

Figure 3. Schematic presentation of achiral components of rotaxanes

图4. 机械面手性轮烷的示意图及分子实例

Figure 4. Schematic presentation and molecular examples of MPC rotaxanes

图5. 机械轴手性轮烷的示意图及分子实例

Figure 5. Schematic presentation and molecular examples of MAC rotaxanes

图6. 两种机械几何异构体轮烷

Figure 6. Two distinct MGI rotaxanes

图7. 两种类型共构象机械手性轮烷

Figure 7. Two distinct types of co-conformationally mechanically chiral rotaxane

图式1. 轴体上具有不同站点的轮烷

Scheme 1. Rotaxane with different stations at the axle

图式2. 缝接法和封端法合成轮烷的示意图

Scheme 2. Schematic presentation of the clipping and capping method for rotaxane synthesis

图式3. 通过在配体末端烯丙基使用烯烃关环复分解反应生成轮烷

Scheme 3. Generation of a rotaxane by the use of RCM on the allylic groups of the ligand

图式4. O-酰化封端制备轮烷

Scheme 4. Preparation of rotaxanes via O-acylation

图式5. 金属主动模板合成法制备轮烷的示意图

Scheme 5. Schematic presentation of active metal template synthesis of rotaxanes

图式6. 主动模板铜催化叠氮化物-炔烃环加成反应合成轮烷

Scheme 6. CuAAC active metal template synthesis of rotaxane

图式7. 无金属主动模板制备轮烷的示意图

Scheme 7. Schematic presentation of metal-free active template synthesis of rotaxanes

图式8. 冠醚加速N-酰化反应形成轮烷

Scheme 8. Rotaxane formation by crown-ether-accelerated N-acylation

图式9. N-酰化活性模板合成轮烷

Scheme 9. Active template rotaxane synthesis through N-acylation

图式10. 机械点手性轮烷12的合成

Scheme 10. Synthesis of mechanically point-chiral rotaxane 12

图式11. 带有葡萄糖单元的手性叠氮化合物合成机械面手性轮烷14

Scheme 11. Synthesis of MPC rotaxane 14 from a chiral azide with glucose unit

图式12. 由手性叠氮化合物合成机械面手性轮烷16

Scheme 12. Synthesis of MPC rotaxane 16 from a chiral azide

图式13. 由手性大环合成机械面手性轮烷18

Scheme 13. Synthesis of MPC rotaxane 18 from a chiral macrocycle

图式14. 利用手性互锁辅助策略合成机械面手性轮烷

Scheme 14. Synthesis of MPC rotaxanes using the chiral interlocking auxiliary strategy

图式15. 由含有手性离去基团的活性酯对映选择性合成机械面手性轮烷

Scheme 15. Enantioselective synthesis of MPC rotaxane from activated ester with a chiral leaving group

图式16. 由手性叠氮化合物分步合成机械轴手性轮烷3

Scheme 16. Stepwise synthesis of MAC rotaxane 3 from a chiral azide

图式17. 由手性叠氮化合物直接合成机械轴手性轮烷24

Scheme 17. Direct synthesis of enantioenriched MAC rotaxane 24 from a chiral azide

图式18. 机械点手性轮烷的催化对映选择性合成

Scheme 18. Catalytic enantioselective synthesis of mechanically point-chiral rotaxanes

图式19. 不对称酰化合成机械面手性轮烷

Scheme 19. Synthesis of MPC rotaxane through asymmetric acylation

图式20. 机械面手性轮烷外消旋体的动力学拆分

Scheme 20. Kinetic resolution of racemic MPC rotaxane

图式21. 通过远端离子相互作用实现催化去对称化合成机械面手性轮烷

Scheme 21. MPC rotaxanes through catalytic desymmetrization enabled by distal ionic interactions

图式22. 机械点手性轮烷(S)-12催化的醛的不对称α-胺化反应

Scheme 22. Asymmetric α-amination of aldehydes catalyzed by rotaxane (S)-12

图式23. 机械面手性轮烷30催化的不对称环丙烷化反应

Scheme 23. Enantioselective cyclopropanation reaction catalyzed by MPC rotaxane 30

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