Small organic molecules with tailored structures: initiators in the transition-metal-free C–H arylation of unactivated arenes

Zhenghui Liu; Peng Wang; Yu Chen; Zhenzhong Yan; Suqing Chen; Wenjun Chen; Tiancheng Mu

doi:10.1039/D0RA01845G

Small organic molecules with tailored structures: initiators in the transition-metal-free C–H arylation of unactivated arenes†

Zhenghui Liu,

*^a Peng Wang,^bc Yu Chen,

^d Zhenzhong Yan,^a Suqing Chen,^a Wenjun Chen^e and Tiancheng Mu

*^e

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* Corresponding authors

^a School of Pharmaceutical and Materials Engineering, Taizhou University, Taizhou 318000, Zhejiang, China
E-mail: liuzhenghui@iccas.ac.cn

^b Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

^c Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China

^d Department of Chemistry and Material Science, Langfang Normal University, Langfang 065000, Hebei, China

^e Department of Chemistry, Renmin University of China, Beijing 100872, China
E-mail: tcmu@ruc.edu.cn

Abstract

Simple, small organic molecules containing nitrogen and oxygen atoms in their structures have been disclosed to catalyze transition-metal-free C–H arylation of unactivated arenes with aryl iodides in the presence of ^tBuOK. In this article, an optimized catalytically active molecule, (2-(methylamino)phenyl)methanol, was designed. A broad range of aryl iodides could be converted into the corresponding arylated products at 100 °C over 24 h with good to excellent yields. Mechanistic experiments verified that radicals participated in this catalytic transformation and that the cleavage of the aromatic C–H bond was not the rate determining step. A K⁺ capture experiment by 18-crown-6 emphasized the significance of the cation species of the strong base. Fourier transform infrared spectroscopy proved that the catalytic system was activated by the hydrogen bonds between small organic molecules and ^tBuOK. Also, a clear mechanism was proposed. This transition-metal-free method affords a promising system for efficient and inexpensive synthesis of biaryls via a user-friendly approach, as confirmed by scale-up experiments.

This article is part of the themed collection: Organic chemist’s toolbox

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Small organic molecules with tailored structures: initiators in the transition-metal-free C–H arylation of unactivated arenes†

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Small organic molecules with tailored structures: initiators in the transition-metal-free C–H arylation of unactivated arenes

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