Bioinspired Transformations Using Strictosidine Aglycones: Divergent Total Syntheses of Monoterpenoid Indole Alkaloids in the Early Stage of Biosynthesis
Bioinspired Transformations Using Strictosidine Aglycones: Divergent Total Syntheses of Monoterpenoid Indole Alkaloids in the Early Stage of Biosynthesis
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使用胡桃苷苷元的仿生转化：生物合成早期阶段单萜吲哚生物碱的不同全合成
DOI：
10.1002/chem.202104052
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Hayato Ishikawa
中科院分区：
文献类型：
--
作者：
Jukiya Sakamoto;Hayato Ishikawa
报道了一系列生物灵感转化方法，将严格苷元转化为单萜吲哚生物碱。通过简单地从硅醚衍生物中去除硅基保护基团，原位制备了高活性的关键中间体--严格苷元，并在底物控制下通过生物激发转化选择性地转化为杂亨宾和箭毒碱型，以及阿卡格林和核核苷相关生物碱。因此，13种单萜类吲哚生物碱，(−)-天冬氨酸、(−)-四氢山梨碱、(+)-二氢山苍子碱、(−)-山珊瑚碱、(−)-阿卡格林、(−)-二氢环阿拉伯碱碱、(−)-核内酯B、(+)-核碱基、(−)-核苷D和Ⅲ、(−)-核丝氨酸和(−)-核糖核酰胺A和E，在不到13个 步骤中完成了简明、发散的全合成。
A series of bioinspired transformations that are applied to convert strictosidine aglycones into monoterpenoid indole alkaloids is reported. The highly reactive key intermediates, strictosidine aglycones, were prepared in situ by simple removal of a silyl protecting group from the silyl ether derivatives, and converted selectively via bioinspired transformations under substrate control into heteroyohimbine‐ and corynantheine‐type, and akagerine and naucleaoral related alkaloids. Thus, concise, divergent total syntheses of 13 monoterpenoid indole alkaloids, (−)‐cathenamine, (−)‐tetrahydroalstonine, (+)‐dihydrocorynantheine, (−)‐corynantheidine, (−)‐akagerine, (−)‐dihydrocycloakagerine, (−)‐naucleaoral B, (+)‐naucleidinal, (−)‐naucleofficines D and III, (−)‐nauclefiline, and (−)‐naucleamides A and E, were accomplished in fewer than 13 steps.