Citation: Taixin Yang, Yuanyuan Huang, Yingchao Dou, Yanbo Zhang, Baohe Yang, Dandan Yang, Jun-Long Niu. Atropisomeric synthesis of multiple C–N or N–N axially chiral calix[4]arenes through cobalt-catalyzed multisite C–H activation/annulation[J]. Chinese Chemical Letters, ;2026, 37(12): 112436. doi: 10.1016/j.cclet.2026.112436 shu

Atropisomeric synthesis of multiple C–N or N–N axially chiral calix[4]arenes through cobalt-catalyzed multisite C–H activation/annulation

Taixin Yang ^{a, 1} ,
Yuanyuan Huang ^{a, 1} ,
Yingchao Dou ^{a, *,} ,
Yanbo Zhang ^a ,
Baohe Yang ^c ,
Dandan Yang ^{a, *,} ,
Jun-Long Niu ^{a, b, **,}

a.
College of Chemistry, Pingyuan Laboratory, Zhengzhou University, Zhengzhou 450001, China
b.
State Key Laboratory of Coking Coal Resources Green Exploitation, Zhengzhou University, Zhengzhou 450001, China
c.
Intelligent Construction School, Zhengzhou Business University, Zhengzhou 451200, China

^**

yingchaodou@zzu.edu.cn

yangdandan@zzu.edu.cn

niujunlong@zzu.edu.cn

Received Date: 26 September 2025
Revised Date: 6 January 2026
Accepted Date: 19 January 2026
Available Online: 20 January 2026

Figures(6)

The construction of molecules with multiple stereogenic axes has garnered growing attention due to their wide potential applications in natural products, pharmaceuticals, functional materials, and asymmetric catalysis. However, the enantioselective synthesis of such skeletons remains underdeveloped, as simultaneous control over diastereo- and enantioselectivity in assembling multiple stereogenic axes poses significant challenges. Reported methodologies mainly focuse on the atropisomeric synthesis of biaxial molecules, while the asymmetric construction of multiaxial systems with more than two stereogenic axes remains in its fancy. Herein, we report an enantioselective one-step synthesis of atropisomeric calix[4]arenes bearing four chiral C–N or N–N axes through an efficient cobalt-catalyzed asymmetric multisite C–H activation/annulation strategy. This method accommodates diverse benzamides and calix[4]arenes, efficiently constructing four C–N or N–N axes on the calix[4]arene scaffold in high yields and excellent stereoselectivities. The absolute stereochemistry was precisely controlled by employing different ligand enantiomers, enabling access to both product enantiomers. The resulting multiaxial atropisomers exhibit a well-defined bowl-shaped architecture and outstanding optical properties, as demonstrated by fluorescence emission, circular dichroism, circularly polarized luminescence studies, and chiral recognition. This work not only demonstrates the robustness of cobalt catalysis in synthesizing complex stereogenic frameworks but also highlights the applications of atropisomeric multiaxes compounds in optical materials.
- Multiple C–N or N–N axially chiral frameworks,
- One-step synthesis,
- Cobalt catalyzed C–H activation,
- Asymmetric synthesis
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