Shenzhen Grubbs Institute and Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, 518055, Shenzhen, China.
Nat Commun. 2020 Jul 15;11(1):3538. doi: 10.1038/s41467-020-17350-x.
Ever since Hirata's report of yuzurimine in 1966, nearly fifty yuzurimine-type alkaloids have been isolated, which formed the largest subfamily of the Daphniphyllum alkaloids. Despite extensive synthetic studies towards this synthetically challenging and biologically intriguing family, no total synthesis of any yuzurimine-type alkaloids has been achieved to date. Here, the first enantioselective total synthesis of (+)-caldaphnidine J, a highly complex yuzurimine-type Daphniphyllum alkaloid, is described. Key transformations of this approach include a highly regioselective Pd-catalyzed hydroformylation, a samarium(II)-mediated pinacol coupling, and a one-pot Swern oxidation/ketene dithioacetal Prins reaction. Our approach paves the way for the synthesis of other yuzurimine-type alkaloids and related natural products.
自 1966 年平田报告羽扇豆碱以来，已分离出近五十种羽扇豆碱型生物碱，形成了瑞香科生物碱中最大的亚科。尽管对这个具有挑战性的合成和具有生物吸引力的家族进行了广泛的合成研究，但迄今为止尚未实现任何羽扇豆碱型生物碱的全合成。在此，描述了具有高度复杂羽扇豆碱型瑞香科生物碱（+）-卡达普宁 J 的首次对映选择性全合成。该方法的关键转化包括高度区域选择性的 Pd 催化氢甲酰化、钐（II）介导的频哪醇偶联以及一锅 Swern 氧化/烯酮二硫代缩醛 Prins 反应。我们的方法为合成其他羽扇豆碱型生物碱和相关天然产物铺平了道路。
