Cyclopropenes for the Stepwise Synthesis of 1,2,4,5-Tetraarylbenzenes via 1,4-Cyclohexadienes

Satoshi Kishida; Misaki Takano; Takuya Sekiya; Yutaka Ukaji; Kohei Endo

doi:10.1021/acs.joc.2c01261

Cyclopropenes for the Stepwise Synthesis of 1,2,4,5-Tetraarylbenzenes via 1,4-Cyclohexadienes

J Org Chem. 2022 Nov 4;87(21):14833-14839. doi: 10.1021/acs.joc.2c01261. Epub 2022 Oct 6.

Authors

Satoshi Kishida¹, Misaki Takano¹, Takuya Sekiya², Yutaka Ukaji², Kohei Endo¹

Affiliations

¹ Department of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo 162-8601, Japan.
² Division of Material Chemistry, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan.

Abstract

This paper describes a synthetic approach to the synthesis of 1,2,4,5-tetraarylbenzene derivatives from cyclopropenes. The Lewis acid-mediated dimerization of cyclopropenes gives tricyclo[3.1.0.0^2,4]hexane derivatives. The subsequent thermal ring-opening reaction under solvent-free conditions gives 1,4-cyclohexadienes bearing quaternary carbons. The novel Br₂-mediated oxidative rearrangement of 1,4-cyclohexadienes takes place to give 1,2,4,5-tetraarylbenzene derivatives in high to excellent yields.