Total synthesis and revised structure of Biyouyanagin A
Total synthesis and revised structure of Biyouyanagin A
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DOI：
10.1002/anie.200701552
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Shaw, David M.
中科院分区：
文献类型：
--
作者：
Nicolaou, K. C.;Sarlah, David;Shaw, David M.
意义：Biyouyanagin A从日本民间药材金丝桃（Hypericum chinense L. var. salicifolium）中分离得到。选择性抑制HIV在H9淋巴细胞中的复制，治疗指数大于31.3。本文报道了在C17， C18和C24位点上修改立体化学的12步全合成biyouyanagin A。评论：二酮A与乙炔通过螯合控制反应得到丙炔醇C为主要产物。[2+ 2]- J和K之间的光诱导环加成通过外端过渡态立体选择性地得到了biyouyanagin A作为唯一的产物，因为内端过渡态存在位阻。
Significance: Biyouyanagin A is isolated from Hypericum chinense L. var. salicifolium, a plant used as a folk medicine in Japan. It selectively inhibits the HIV replication in H9 lymphocytes and has got a therapeutic index of greater than 31.3. A 12-step total synthesis of biyouyanagin A with the revised stereochemistry at C17, C18, and C24 is reported here.Comment: Reaction of diketone A with acetylene was directed by chelation control to afford propargylic alcohol C as a major product.[2+ 2]-Photoinduced cycloaddition between J and K stereoselectively gave biyouyanagin A as the only product via an exo transition state, as the endo transition state suffers from steric congestion.