Citation: Jianing Zhang, Weitao Guo, Chaoyang Li, Rongyu Yan, Yunlong Qin, Yang Zhao, Yong-Yuan Gui, Lili Zhao, Qilin Wang. Direct transformation of azaarenes into aromatic aldehydes and QUINAP-like atropisomers[J]. Chinese Chemical Letters, ;2026, 37(8): 112017. doi: 10.1016/j.cclet.2025.112017 shu

Direct transformation of azaarenes into aromatic aldehydes and QUINAP-like atropisomers

Jianing Zhang ^{a, 1} ,
Weitao Guo ^{b, 1} ,
Chaoyang Li ^{a, 1} ,
Rongyu Yan ^b ,
Yunlong Qin ^a ,
Yang Zhao ^a ,
Yong-Yuan Gui ^c ,
Lili Zhao ^{b, *,} ,
Qilin Wang ^{a, *,}

a.
College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, China
b.
State Key Laboratory of Materials-Oriented Chemical Engineering, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China
c.
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China

ias_llzhao@njtech.edu.cn

wangqilin@henu.edu.cn

Received Date: 3 September 2025
Revised Date: 13 October 2025
Accepted Date: 22 October 2025
Available Online: 24 October 2025

Figures(7)

A significant challenge in organic synthesis has been the direct transformation of azaarenes into synthetically important aromatic aldehydes via formal nitrogen extrusion and carbon insertion. In this study, we present an efficient approach to reshape easily accessible azaarene-based onium salts, such as isoquinoliniums, pyridiniums, and pyrimidiniums, into functionalized multi-substituted aromatic aldehydes. This strategy relies on the strategic use of an inverse-electron-demand [4 + 2] cycloaddition-inspired cascade process with a wide tolerance of allenes, alkynes or alkenes as dienophiles. DFT calculations were conducted to gain insight into the reaction mechanism, revealing the significant catalytic roles of Na₂CO₃ and H₂O for aldehyde formation and deamination. The operational simplicity enables widespread application of this strategy which has successfully been expanded towards the direct transformation of fused pyridinium and isoquinolinium salts as well as naturally occurring pharmaceuticals berberine sulfate and palmatine chloride into structurally novel atropisomeric N/P compounds. The resultant N/P compounds have demonstrated their potential application as ligands.
- Skeletal editing,
- Atom exchange,
- Azaarenes,
- Aromatic aldehydes,
- Atropisomers
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