Ni-Catalyzed Cycloisomerization between 3-Phenoxy Acrylic Acid Derivatives and Alkynes via Intramolecular Cleavage and Formation of the C-O Bond To Give 2,3-Disubstituted Benzofurans

Shohei Ohno; Jiawei Qiu; Ray Miyazaki; Hiroshi Aoyama; Kenichi Murai; Jun-Ya Hasegawa; Mitsuhiro Arisawa

doi:10.1021/acs.orglett.9b03170

Ni-Catalyzed Cycloisomerization between 3-Phenoxy Acrylic Acid Derivatives and Alkynes via Intramolecular Cleavage and Formation of the C-O Bond To Give 2,3-Disubstituted Benzofurans

Org Lett. 2019 Oct 18;21(20):8400-8403. doi: 10.1021/acs.orglett.9b03170. Epub 2019 Oct 1.

Authors

Shohei Ohno¹, Jiawei Qiu¹, Ray Miyazaki², Hiroshi Aoyama¹, Kenichi Murai¹, Jun-Ya Hasegawa², Mitsuhiro Arisawa¹

Affiliations

¹ Graduate School of Pharmaceutical Sciences , Osaka University , Yamada-oka 1-6 , Suita , Osaka 565-0871 , Japan.
² Institute for Catalysis , Hokkaido University , Kita 21 Nishi 10, Kita-ku , Sapporo , Hokkaido 001-0021 , Japan.

PMID: 31573210
DOI: 10.1021/acs.orglett.9b03170

Abstract

Reactions based on transition-metal-catalyzed C-O bond cleavage have attracted much attention as a new synthetic method. Until now, several intermolecular reactions via C-O bond cleavage of aryl ethers, alkenyl ethers, esters, and others have been reported. Here we report an unprecedented C-O bond cleavage of 3-phenoxy acrylic acid derivatives, followed by intramolecular C-O bond formation with alkynes. This reaction gave 2,3-disubstituted benzofurans having useful functional groups-silyl substituents and acrylic acid derivatives-at the 2- and 3-positions, respectively. This report also described theoretical (DFT) insights into the mechanism.