Biomimetic Synthesis of Macahydantoins A and B from Lepidium meyenii, and Structure Revision of Macahydantoin B as a Class of Thiohydantoin with a 4-Methyl-hexahydropyrrolo[1,2-c]imidazole Skeleton.
Biomimetic Synthesis of Macahydantoins A and B from Lepidium meyenii, and Structure Revision of Macahydantoin B as a Class of Thiohydantoin with a 4-Methyl-hexahydropyrrolo[1,2-c]imidazole Skeleton.
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DOI：
10.1021/acs.orglett.7b02433
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发表时间：
2017-09
期刊：
影响因子：
5.2
通讯作者：
Min Zhou;Hang-Ying Ma;Huan-huan Xing;Ping Li;Gan-peng Li;Hui-Chun Geng;Qiu-Fen Hu;Guangyu Yang
中科院分区：
文献类型：
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作者：
Min Zhou;Hang-Ying Ma;Huan-huan Xing;Ping Li;Gan-peng Li;Hui-Chun Geng;Qiu-Fen Hu;Guangyu Yang
对玛卡海因C（3）的植物化学研究发现了玛卡海因C（3），这是一种新的具有1，3-二氮杂双环[3.3.1]壬烷核的硫代海因，其光谱性质表明其以前报道的类似物玛卡海因B（2a）可能存在结构错误。为了探索这一假设，使用改进的Edman降解作为关键步骤，从市售材料有效地完成了最初提出的2a及其修订结构（2b）的简洁、可扩展和仿生合成，总产率分别为65%（三步）和52%（三步）。这些合成的努力无疑重新分配的结构macahyantoin B作为一种未报道的类型的硫代乙内酰脲特征的4-甲基-六氢吡咯并[1，2-c]咪唑支架。
Phytochemical investigation on Lepidium meyenii led to the discovery of macahydantoin C (3), a new thiohydantoin with a 1,3-diazabicyclo[3.3.1]nonane core, the spectral properties of which indicate a potential structural misassignment of its previously reported analogue, macahydantoin B (2a). To probe this hypothesis, a concise, scalable, and biomimetic synthesis of the originally proposed 2a and its revised structure (2b) was efficiently accomplished using the modified Edman degradation as the key step from commercially available materials in 65% (three steps) and 52% (three steps) overall yields, respectively. These synthetic endeavors undoubtedly reassigned the structure of macahydantoin B as an unreported type of thiohydantoin featuring a 4-methyl-hexahydropyrrolo[1,2-c]imidazole scaffold.