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Updated: Oct 31, 2025

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Metal-free dearomative [5+2]/[2+2] cycloaddition of 1H-indoles with ortho-(trimethylsilyl)aryl triflates
Xinyu Chen1, Na Yang1, Wen Zeng1
1Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. China. leiwang88@hotmail.com hongjili@chnu.edu.cn.
Abstract:
Herein, we report a mild dearomative [5+2]/[2+2] cycloaddition of 1H-indoles with ortho-(trimethylsilyl)aryl triflates. The unique [5+2] cycloaddition enables the synthesis of a series of dibenzo[b,e]azepine derivatives in moderate to good yields. Increasing the steric hindrance at the C2-position of 1H-indoles leads to the [2+2] cycloaddition. Mechanistic investigations support that the reaction of 1H-indoles with arynes undergoes a [2+2] cycloaddition step, followed by a ring expansion to the [5+2] cycloaddition product.
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