Synlett 2025; 36(10): 1413-1417
DOI: 10.1055/a-2542-3481
letter

Total Synthesis of Aloin by Regioselective Diels–Alder Reactions Connecting Two 3-Silylbenzynes and a 2-Stannylfuran

Authors

  • Shogo Moriyama

    a   Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan
  • Yuto Emi

    a   Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan
  • Toshifumi Nosaki

    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
  • Yuki Morikawa

    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
  • Takashi Shigeta

    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
    C   School of Food and Nutritional Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
  • Akira Takagi

    d   Kobe Pharmaceutical University, Motoyama-kita, Higashinada-ku, Kobe, Hyogo 658-8558, Japan
  • Masahiro Egi

    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
    C   School of Food and Nutritional Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
  • Takashi Ikawa

    a   Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan
    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan
    e   Gifu Pharmaceutical University, Daigakunishi, Gifu, Gifu 501-1196, Japan
  • Yoshinari Sawama

    a   Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan
  • Shuji Akai

    a   Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan
    b   School of Pharmaceutical Sciences, University of Shizuoka, Yada, Suruga-ku, Shizuoka, Shizuoka 422-8526, Japan

This work was supported by the Research Support Project for Life Science and Drug Discovery [Basis for Supporting Innovative Drug Discovery and Life Science Research (BINDS)] from AMED (Grant Number JP24ama121054) (for Y.S. and S.A.) and JST SPRING (Grant Number JPMJSP2138) (for S.M.).


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Abstract

The first synthesis of aloin, a natural anthrone C-glycoside, was achieved through two sequential Diels–Alder (DA) reactions connecting two 3-silylbenzynes and a 2-stannylfuran. The silyl and stannyl substituents contributed to the regioselectivity of the two DA reactions and the 9,10-ether cleavage of the DA adduct. Subsequent conversion of the silyl groups into hydroxy groups and a C10-glycosylation completed the synthesis of aloin.

Supporting Information



Publication History

Received: 29 December 2024

Accepted after revision: 19 February 2025

Accepted Manuscript online:
19 February 2025

Article published online:
01 April 2025

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