Citation: Yujian Mao, Xiaoting Song, Dandan Yuan, Yaoyu Lin, Junkai You, Yinan Zhang. Transannular C–H functionalizations of polycyclic aromatic compounds by covalently attached directing groups strategy[J]. Chinese Chemical Letters, ;2026, 37(11): 112341. doi: 10.1016/j.cclet.2025.112341 shu

Transannular C–H functionalizations of polycyclic aromatic compounds by covalently attached directing groups strategy

Jiangsu Key Laboratory for Functional Substances of Chinese Medicine, School of Pharmacy, Nanjing University of Chinese Medicine Nanjing, Nanjing 210023, China

yinanzhang@njucm.edu.cn

Received Date: 16 October 2025
Revised Date: 19 December 2025
Accepted Date: 29 December 2025
Available Online: 30 December 2025

Figures(8)

Precisely controlling the regioselectivity on remote C–H bonds of polycyclic aromatic hydrocarbons could rapidly access to unique molecules among natural products, materials and pharmaceuticals. Compared to conventional homoannular C–H functionalizations, heteroannular remote C–H bonds are difficult to reach due to the lack of spatial or electronic biases. Herein, simple, commercially available nitrile-based directing templates have been well-designed to achieve the high-efficient transannular C7-H alkenylation, allylation, and acetoxylation in diverse polycyclic aromatic substrates. Excellent C7-regioselectivity was observed in the presence of the less-sterically but electronically similar C3-H bond. Detailed mechanistic studies revealed that Ag salt acts as co-catalyst in the C–H activation step by facilitating the formation of an active Pd−Ag bimetallic complex. Our findings not only necessitate a practical synthetic approach to useful polycyclic aromatic hydrocarbons and related natural products but also provide mechanistic insights for building hybridized catalysis in the remote C–H activation on (hetero)aromatic systems.
- C–H activation,
- Alkenylation,
- Covalently attached directing groups,
- Pd catalysis,
- Naphthalen
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