Cleavage of non-polar C(sp2)‒C(sp2) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution

Junfeng Lin, Yaxin Lv, Kai Song, Xuwei Song, Hongjun Zang, Pingwu Du, Yaping Zang () and Daoben Zhu
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Junfeng Lin: Chinese Academy of Sciences
Yaxin Lv: Chinese Academy of Sciences
Kai Song: Chinese Academy of Sciences
Xuwei Song: Chinese Academy of Sciences
Hongjun Zang: Tiangong University
Pingwu Du: University of Science and Technology of China
Yaping Zang: Chinese Academy of Sciences
Daoben Zhu: Chinese Academy of Sciences

Nature Communications, 2023, vol. 14, issue 1, 1-7

Abstract: Abstract Electrophilic aromatic substitution (EAS) is one of the most fundamental reactions in organic chemistry. Using an oriented external electric field (OEEF) instead of traditional reagents to tune the EAS reactivity can offer an environmentally friendly method to synthesize aromatic compounds and hold the promise of broadening its scope. Despite these advantages, OEEF catalysis of EAS is difficult to realize, due to the challenge of microscopically orienting OEEF along the direction of electron reorganizations. In this work, we demonstrate OEEF-catalyzed EAS reactions in a series of cycloparaphenylenes (CPPs) using the scanning tunneling microscope break junction (STM-BJ) technique. Crucially, the unique radial π-conjugation of CPPs enables a desired alignment for the OEEF to catalyze the EAS with Au STM tip (or substrate) acting as an electrophile. Under mild conditions, the OEEF-catalyzed EAS reactions can cleave the inherently inert C(sp2)-C(sp2) bond, leading to high-yield (~97%) formation of linear oligophenylenes terminated with covalent Au-C bonds. These results not only demonstrate the feasibility of OEEF catalysis of EAS, but also offer a way of exploring new mechanistic principles of classic organic reactions aided by OEEF.

Date: 2023
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DOI: 10.1038/s41467-022-35686-4

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