Research Progress in Mechanically Chiral Rotaxanes

doi:10.6023/cjoc202504033

Abstract

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

Cite this article

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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Fig. & Tab. 30

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

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

Figure 3. Schematic presentation of achiral components of rotaxanes

Figure 4. Schematic presentation and molecular examples of MPC rotaxanes

Figure 5. Schematic presentation and molecular examples of MAC rotaxanes

Figure 6. Two distinct MGI rotaxanes

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

Scheme 1. Rotaxane with different stations at the axle

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

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

Scheme 4. Preparation of rotaxanes via O-acylation

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

Scheme 6. CuAAC active metal template synthesis of rotaxane

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

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

Scheme 9. Active template rotaxane synthesis through N-acylation

Scheme 10. Synthesis of mechanically point-chiral rotaxane 12

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

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

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

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

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

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

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

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

Scheme 19. Synthesis of MPC rotaxane through asymmetric acylation

Scheme 20. Kinetic resolution of racemic MPC rotaxane

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

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

Scheme 23. Enantioselective cyclopropanation reaction catalyzed by MPC rotaxane 30

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