Sato Shingo, Hiroe Kaoru, Kumazawa Toshihiro, Jun-ichi Onodera
Department of Chemistry and Chemical Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan.
Carbohydr Res. 2006 Jul 3;341(9):1091-5. doi: 10.1016/j.carres.2006.03.038. Epub 2006 Apr 27.
Genistein and orobol 8-C-beta-D-glucopyranosides (1 and 3) were firstly synthesized in overall yields of 39% and 41% from 2,4-di-O-benzylphloroacetophenone (4), as follows: (1) the formation of the chalcone (6, 7) by aldol condensation of the benzyl-protected C-glycosylphloroacetophenone (5), a key intermediate of the total synthesis of 1 and 3 and synthesized by a C-glycosylation method involving the O-->C glycoside rearrangement of 4 in 96% yield; (2) the formation of isoflavones (10, 11 and 12, 13) by the formation of acetals by oxidative rearrangement of the protected chalcones (8 and 9) using Tl(NO3)3, followed by acid-catalyzed cyclization; (3) a final debenzylation by hydrogenolysis.
染料木黄酮和刺芒柄花素8 - C - β - D - 吡喃葡萄糖苷（1和3）首次以2,4 - 二 - O - 苄基间苯三酚乙酮（4）为原料，总产率分别为39%和41%合成，具体步骤如下：（1）通过苄基保护的C - 糖基间苯三酚乙酮（5）的羟醛缩合反应形成查耳酮（6, 7），5是1和3全合成的关键中间体，通过涉及4的O→C糖苷重排的C - 糖基化方法以96%的产率合成；（2）使用硝酸铊通过保护的查耳酮（8和9）的氧化重排形成缩醛，然后进行酸催化环化反应，形成异黄酮（10, 11和12, 13）；（3）通过氢解进行最终的脱苄基反应。
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