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

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

Satoshi Kishida  1 , Misaki Takano  1 , Takuya Sekiya  2 , Yutaka Ukaji  2 , Kohei Endo  1
Affiliations

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

Satoshi Kishida et al. J Org Chem. .

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[3.1.0.02,4]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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Synthetic approach to 1,2,4,5-tetraarylbenzenes 4.
Figure 2
Figure 2
Speculated mechanism of the [2 + 2]-type reaction.
Scheme 1
Scheme 1. Oxidative Rearrangement of 3c
Figure 3
Figure 3
Proposed mechanism for dehydrogenative rearrangement.
See this image and copyright information in PMC

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