Issue 25, 2020

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

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
26 feb 2020
Accepted
24 mar 2020
First published
09 apr 2020
This article is Open Access
Creative Commons BY license

RSC Adv., 2020,10, 14500-14509

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

Z. Liu, P. Wang, Y. Chen, Z. Yan, S. Chen, W. Chen and T. Mu, RSC Adv., 2020, 10, 14500 DOI: 10.1039/D0RA01845G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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