Etherification of Fluoroarenes with Alkoxyboronic Acid Pinacol Esters via C-F Bond Cleavage

Jun Zhou; Bingyao Jiang; Zhengyu Zhao; Norio Shibata

doi:10.1021/acs.orglett.2c01864

Etherification of Fluoroarenes with Alkoxyboronic Acid Pinacol Esters via C-F Bond Cleavage

Org Lett. 2022 Jul 22;24(28):5084-5089. doi: 10.1021/acs.orglett.2c01864. Epub 2022 Jul 7.

Authors

Jun Zhou¹, Bingyao Jiang², Zhengyu Zhao¹, Norio Shibata^{1

2}

Affiliations

¹ Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
² Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.

PMID: 35797451
DOI: 10.1021/acs.orglett.2c01864

Abstract

Potassium-base-mediated defluoroetherification of aryl and heteroaryl fluorides with alkoxyboronic acid pinacol esters under transition-metal-free conditions is reported. This protocol efficiently and safely provides a wide variety of aryl ethers in high yields without using metal catalysts, specific ligands, and harsh conditions to selectively forge C_sp2-O bonds via the C_sp2-F cleavage. This method can be applied to the late-stage etherification of structurally complex C_sp2-fluorides and bioactive alcohols, such as β-estradiol, calciferol, and tocopherol.