Citation: Yan-E Zhang, Yingtao Jiang, Yun Zhang, Hu Wang, Zitong Wu, Rui Li, Yumiao Ma, Tao Tu. Enantioselective synthesis of bulky planar-chiral pillar[n]arenes through dynamic kinetic resolution[J]. Chinese Chemical Letters, ;2025, 36(12): 111201. doi: 10.1016/j.cclet.2025.111201 shu

Enantioselective synthesis of bulky planar-chiral pillar[n]arenes through dynamic kinetic resolution

Yan-E Zhang ^{a, *,} ,
Yingtao Jiang ^a ,
Yun Zhang ^a ,
Hu Wang ^a ,
Zitong Wu ^a ,
Rui Li ^a ,
Yumiao Ma ^{b, *,} ,
Tao Tu ^{a, c, *,}

a.
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China
b.
BSJ Institute, Beijing 100084, China
c.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

^**

zhangyane@nxu.edu.cn

ymma@bsj-institute.top

taotu@fudan.edu.cn

Received Date: 26 March 2025
Revised Date: 9 April 2025
Accepted Date: 11 April 2025
Available Online: 18 April 2025

Figures(6)

The precise synthesis of planar chiral pillar[n]arenes (PAs) faces significant challenges due to their inherent dynamic racemization induced by rapid molecular flipping. To address this issue and enhance conformational stability of these macrocycles, we have developed a strategic approach involving the introduction of sterically bulky aryl (sp²) substituents at the molecular rims through dynamic kinetic resolution (DKR). A series of robust and chirality-aligned homo- and hetero-diaryl PAs (n = 5, 6) were achieved with excellent enantioselectivity (>95% ee) via Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions. Mechanism study revealed axial steric hindrance, rather than radial substitution, governs conformational chirality-locking in pillar[n]arenes. This work not only provides an attractive protocol for the enantioselective synthesis of planar chiral pillar[n]arenes, but also enriches the library of macrocycles for promising applications in chiral molecular machines, enantioselective sensors, and chiral luminescent materials.
- Dynamic kinetic resolution,
- Pd-catalysis,
- Planar chirality,
- Pillararenes,
- Suzuki–Miyaura cross-coupling
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