Zhan Tangyu, Zhou Liang, Zhou Yuqiao, Yang Bingqian, Feng Xiaoming, Liu Xiaohua
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University Chengdu 610064 P. R. China
Chem Sci. 2024 Feb 29;15(13):4797-4803. doi: 10.1039/d4sc00078a. eCollection 2024 Mar 27.
The asymmetric catalytic inverse-electron-demand hetero-Diels-Alder reaction of dioxopyrrolidines with a variety of simple olefins has been accomplished, significantly expanding the applicability of this cyclization to both cyclic hetero-dienes and dienophiles. A new type of strong Lewis acid catalyst of ferric salt enables the LUMO activation of dioxopyrrolidines formation of cationic species, this method yields a range of bicyclic dihydropyran derivatives with exceptional outcomes, including high yields (up to 99%), diastereoselectivity (up to 99 : 1) and enantioselectivity (up to 99% ee) under mild conditions. This facile protocol was available for the late-stage modification of several bioactive molecules and transformation into macrocycle molecules as well. The origins of enantioselectivity were elucidated based on control experiments.
已实现二氧代吡咯烷与多种简单烯烃的不对称催化逆电子需求杂Diels-Alder反应，显著扩展了这种环化反应对环状杂二烯和亲双烯体的适用性。一种新型的铁盐强路易斯酸催化剂能够实现二氧代吡咯烷的LUMO活化并形成阳离子物种，该方法能在温和条件下得到一系列双环二氢吡喃衍生物，产率高（高达99%）、非对映选择性高（高达99∶1）且对映选择性高（高达99% ee），结果优异。这种简便的方法可用于几种生物活性分子的后期修饰，也可转化为大环分子。基于对照实验阐明了对映选择性的起源。
