Biomimetic Synthesis of the CDE Ring Moiety of Physalins, Complex 13,14-Secosteroids
Biomimetic Synthesis of the CDE Ring Moiety of Physalins, Complex 13,14-Secosteroids
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DOI：
10.1021/acs.orglett.0c04198
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发表时间：
2021-01-14
期刊：
影响因子：
5.2
通讯作者：
Nishikawa, Toshio
中科院分区：
文献类型：
--
作者：
Araki, Yusuke;Nakazaki, Atsuo;Nishikawa, Toshio
酸浆素是从酸浆属中分离的结构复杂的13，14-开环甾体家族。我们公开了基于我们的生物合成方案从带有14-OH、18-COOMe和17，20-α-环氧化物的甾体化合物两步构建酸浆素的CDE环部分。C13-C14键在C-14处被烷氧基裂解，并且自发的环氧化物开环得到具有环壬烯和γ-内酯的化合物。非对映选择性的二羟基化所得的烯烃与OsO 4提供的CDE环部分酸浆素。
Physalins are a structurally complex family of 13,14-secosteroids isolated from the genus Physalis. We disclose a two-step construction of the CDE ring moiety of the physalins from a steroidal compound bearing 14-OH, 18-COOMe, and 17, 20-alpha-epoxide based on our biosynthetic proposal. C13-C14 bond cleavage by an alkoxy radical at C-14 and spontaneous epoxide ring opening gave a compound having a cyclononene and gamma-lactone. Diastereoselective dihydroxylation of the resulting alkene with OsO4 provided the CDE ring moiety of physalin.