Total synthesis of aspergillide B and structural discrepancy of aspergillide A
Total synthesis of aspergillide B and structural discrepancy of aspergillide A
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DOI：
10.1016/j.tetlet.2008.10.115
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发表时间：
2009-01-14
影响因子：
1.8
通讯作者：
Uenishi, Jun'ichi
中科院分区：
文献类型：
--
作者：
Hande, Sudhir M.;Uenishi, Jun'ichi
利用zeta-羟基手性烯丙醇7的立体定向Pd（II）催化环化反应，从醇10经15步合成了14元细胞毒性大环内酯1和2。从海洋真菌中分离得到两个新化合物A和B，结构分别为1和2。合成的1与曲霉素A不匹配，但与曲霉素B匹配。曲霉内酯B C-13位的手性中心被修正为（S）-构型。立体选择性合成的关键步骤包括Sharpless不对称双羟基化、交叉复分解、Pd-II催化下16位四氢吡喃环的立体选择性构建和Yamaguchi大环内酯化。(C)2008爱思唯尔有限公司版权所有。
Fourteen-membered cytotoxic macrolides 1 and 2 were synthesized from alcohol 10 in 15 steps utilizing stereospecific Pd(II)-catalyzed cyclization of zeta-hydroxy chiral allylic alcohol 7. Aspergillides A and B were isolated from marine fungus, and their structures were proposed as 1 and 2, respectively. The synthetic 1 was not matched with aspergillide A but matched with aspergillide B. The chiral center at C-13 position of aspergillide B was revised to be(S)-configuration. The key steps of the stereoselective synthesis include the Sharpless asymmetric dihydroxylation, cross-metathesis, stereospecific construction of tetrahydropyran ring of 16 using Pd-II catalyst, and the Yamaguchi macrolactonization. (C) 2008 Elsevier Ltd. All rights reserved.