Synthesis of 9,10-Diarylanthracenes via Mg(TMP)2·2LiCl-Mediated Benzyne Generation/[4+2] Cycloaddition and Deoxygenation of 9,10-Epoxyanthracene Intermediates

Naoya Miyamoto; Yuki Nakazawa; Takanori Nakamura; Kentaro Okano; Sota Sato; Zhe Sun; Hiroyuki Isobe; Hidetoshi Tokuyama

doi:10.1055/s-0036-1591510

Synlett, Table of Contents

Synlett 2018; 29(04): 513-518
DOI: 10.1055/s-0036-1591510

letter

Synthesis of 9,10-Diarylanthracenes via Mg(TMP)₂·2LiCl-Mediated Benzyne Generation/[4+2] Cycloaddition and Deoxygenation of 9,10-Epoxyanthracene Intermediates

Naoya Miyamoto

^aGraduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, 980-8578, Japan Email: tokuyama@m.tohoku.ac.jp

,

Yuki Nakazawa

^aGraduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, 980-8578, Japan Email: tokuyama@m.tohoku.ac.jp

,

Takanori Nakamura

^aGraduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, 980-8578, Japan Email: tokuyama@m.tohoku.ac.jp

,

Kentaro Okano

^aGraduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, 980-8578, Japan Email: tokuyama@m.tohoku.ac.jp

,

Sota Sato

^bDepartment of Chemistry, The University of Tokyo and JST, ERATO, Isobe Degenerate π-Integration Project, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan

,

Zhe Sun

^bDepartment of Chemistry, The University of Tokyo and JST, ERATO, Isobe Degenerate π-Integration Project, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan

,

Hiroyuki Isobe

^bDepartment of Chemistry, The University of Tokyo and JST, ERATO, Isobe Degenerate π-Integration Project, Hongo 7-3-1, Bunkyo-ku, Tokyo, 113-0033, Japan

,

Hidetoshi Tokuyama*

^aGraduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, 980-8578, Japan Email: tokuyama@m.tohoku.ac.jp

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Abstract

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^§ These authors contributed equally

Abstract

A new synthetic route to functionalized 9,10-diarylanthracenes has been developed. 9,10-Epoxyanthracene intermediates were prepared by [4+2] cycloaddition of 1,3-diarylisobenzofuran with a variety of functionalized benzyne intermediates, which were obtained by Mg(TMP)₂·2LiCl-mediated benzyne generation. For the cleavage of the resultant 9,10-epoxyanthracene intermediates, we developed mild deoxygenation conditions using a combination of trifluoroacetic acid and Et₃SiH. The utility of this sequence was demonstrated by application to the synthesis of 5,7,12,14-tetraphenylpentacene.

Key words

anthracene - pentacene - arynes - cycloaddition - furanes - deoxygenation

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References

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Supplementary Material

Supporting Information