Total Synthesis of the Claimed Structure of (±)-Hyptinin and Structural Revision of Natural Hyptinin
Total Synthesis of the Claimed Structure of (±)-Hyptinin and Structural Revision of Natural Hyptinin
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DOI：
10.1021/acs.jnatprod.6b01116
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发表时间：
2017-05-01
影响因子：
5.1
通讯作者：
Okamura, Hiroaki
中科院分区：
文献类型：
--
作者：
Maeda, Kazuto;Hamada, Toshiyuki;Okamura, Hiroaki
以膦酸酯、环酮和芳基格氏试剂为主要原料，采用收敛路线合成了（+/-）-海替宁。天然产物的H-1和C-13 NMR谱与合成产物的H-1和C-13 NMR谱不一致。特别是，天然和合成的化合物的内酯羰基周围的质子和碳的信号之间有相当大的差异。核磁共振数据强烈表明，天然存在的化合物，海替宁，是合成化合物的结构异构体。根据合成结果，该天然化合物的结构最终确定为（+）-β-apopicropodophyllin。
A total synthesis of (+/-)-hyptinin was achieved via a convergent route using the key phosphonate, cyclic ketone, and aryl Grignard components. The H-1 and C-13 NMR spectra of natural hyptinin did not agree with those of the synthesized compound. In particular, there were considerable differences between the signals assigned to the protons and carbons surrounding the lactone carbonyl group for the natural and synthesized compounds. The NMR data strongly suggested that the naturally occurring compound, hyptinin, was a structural isomer of the synthesized compound. The structure of the natural compound was eventually established as (+)-beta-apopicropodophyllin, based on the synthesis results.