Citation: Guang-Hui Wang, Jia-Tian Jiang, Jian Yang, Ze-Shu Wang, Gongde Wu, Long-Wu Ye, Bo Zhou. Brønsted acid-catalyzed atroposelective desymmetrization of diamines with carboxylic acids via ynamide-mediated amidation[J]. Chinese Chemical Letters, ;2026, 37(10): 112278. doi: 10.1016/j.cclet.2025.112278 shu

Brønsted acid-catalyzed atroposelective desymmetrization of diamines with carboxylic acids via ynamide-mediated amidation

Guang-Hui Wang ^{a, 1} ,
Jia-Tian Jiang ^{a, 1} ,
Jian Yang ^a ,
Ze-Shu Wang ^b ,
Gongde Wu ^c ,
Long-Wu Ye ^{a, c, d} ,
Bo Zhou ^{a, e, *,}

a.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
b.
Institute of New Materials & Industry Technology, Wenzhou University, Wenzhou 325000, China
c.
College of Environmental Engineering, Nanjing Institute of Technology, Nanjing 211167, China
d.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
e.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China

zhoubo@xmu.edu.cn

Received Date: 5 September 2025
Revised Date: 2 December 2025
Accepted Date: 12 December 2025
Available Online: 13 December 2025

Figures(6)

Axially chiral diaryl ethers are unique skeletons bearing dual-axial chirality, which have broad applications in biologically active molecules. However, the catalytic atroposelective construction of diaryl ethers is very limited. Atroposelective desymmetrization of prochiral diamines is a straightforward pathway to access C–O axially chiral diaryl ethers, but the direct use of industry feedstock chemicals as desymmetrization reagents is highly challenging. Herein, we report a chiral Brønsted acid-catalyzed desymmetrizing amidation of diamines with carboxylic acids by using ynamide as coupling reagent, enabling the efficient synthesis of C–O and C–C axially chiral anilines. The synthetic utility is demonstrated by one-pot amidation with carboxylic acids, scale-up reaction, synthesis of chiral ligand and catalyst, as well as the applications in asymmetric catalysis. Importantly, this reaction represents a rare atroposelective desymmetrization of diamines with carboxylic acids.
- Atroposelective amidation,
- Carboxylic acid,
- Chiral Brønsted acid,
- C–O axial chirality,
- Ynamide
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