Department of Chemistry and Shenzhen Grubbs Institute , Southern University of Science and Technology , Shenzhen , Guangdong 518055 , China.
State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences , University of Macau , Taipa , Macau 999078 , China.
Org Lett. 2019 Jun 7;21(11):4309-4312. doi: 10.1021/acs.orglett.9b01486. Epub 2019 May 29.
Daphniphyllum alkaloids daphnimacropodines A-C possess a highly congested ring system and share a common tetracyclic ring skeleton. To access the challenging chemical structure of daphnimacropodines, a divergent synthetic approach toward their total synthesis is described. A stereoselective synthesis of the core structure of daphnimacropodines has been achieved from a simple diketone building block. Our approach features an intramolecular carbamate aza-Michael addition and a hydropyrrole synthesis via a Au-catalyzed alkyne hydration followed by an aldol condensation, whereas all the other attempts failed.
三尖杉酯碱生物碱 daphnimacropodines A-C 具有高度拥挤的环系统，并共享一个共同的四环骨架。为了获得 daphnimacropodines 的具有挑战性的化学结构，描述了它们的全合成的一种发散的合成方法。从简单的二酮砌块实现了 daphnimacropodines 的核心结构的立体选择性合成。我们的方法具有分子内氨基甲酸酯氮杂迈克尔加成和通过 Au 催化的炔烃水合随后进行醛缩合的吡咯合成，而所有其他尝试均失败。
