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吲哚二萜Paspalicine、Paspalicine和Paspalicine-13-烯的不对称全合成
作者:小柯机器人 发布时间:2021/11/20 17:06:17

香港科技大学Rongbiao Tong团队报道了吲哚二萜Paspalicine、Paspalicine和Paspalicine-13-烯的不对称全合成。相关研究成果发表在2021年11月16日出版的《德国应用化学》。

Paspaline衍生吲哚二萜(IDTs)是一种结构复杂的真菌毒素,具有独特的致颤活性。

该文报道了三种Paspaline衍生吲哚二萜(IDTs)Paspalicine、Paspalicine和Paspalicine-13-烯的不对称全合成。其合成特点是(1)绿色Achmotowicz重排/双环化,用于高效构建FG环(75%产率)和(2)二烯基级联环闭合复分解,用于高度区域选择性形成CD环(72%产率)。其它亮点包括四个钯介导的反应(Stille、aza-Wacker、Suzuki和Heck)来锻造BE环,以及通过环丙烷的还原开环和共轭酯的α-甲基化来安装两个连续的全碳四元立体中心。

该新合成策略预计将适用于其他Paspaline衍生IDTs的化学合成,并将促进这些农业和药理学重要IDTs的生物活性研究。

附:英文原文

Title: Asymmetric Total Synthesis of Indole Diterpenes Paspalicine, Paspalinine, and Paspalinine-13-ene

Author: Liandong Guo, Zejun Xu, Rongbiao Tong

Issue&Volume: 2021-11-16

Abstract: Paspaline-derived indole diterpenes (IDTs) are structurally complex mycotoxins with unique tremorgenic activity. Reported are asymmetric total syntheses of three paspaline-derived IDTs paspalicine, paspalinine and paspalinine-13-ene. Our synthesis features (1) green Achmatowicz rearrangement/bicycloketalization for efficient construction of FG rings (75% yield) and (2) cascade ring-closing metathesis of dienyne for highly regioselective formation of CD rings (72% yield). Other highlights include four palladium-mediated reactions (Stille, aza-Wacker, Suzuki, and Heck) to forge the BE rings and the installation of two continuous all-carbon quaternary stereocenters via reductive ring-opening of cyclopropane and α-methylation of conjugate ester. Our new synthetic strategy is expected to be applicable to the chemical synthesis of other paspaline-derived IDTs and will facilitate the bioactivity studies of these agriculturally and pharmacologically important IDTs.

DOI: 10.1002/anie.202115384

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202115384

期刊信息

Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx