近日，中国科学院化学研究所杜海峰团队研究了一锅法连续加氢和动力学拆分：两类光学活性N-杂环化合物的同时合成。该研究于2026年1月19日发表在《中国化学》杂志上。

二氢吡咯并[1,2-a]喹喔啉是广泛存在于天然产物及生物活性分子中的重要结构单元。尽管已有多种成熟的外消旋合成策略，但通过不对称催化实现光学活性二氢吡咯并[1,2-a]喹喔啉的对映选择性合成研究仍相对有限。

研究组成功将硼烷催化的吡咯并[1,2-a]喹喔啉氢化反应，与手性磷酸催化的外消旋二氢吡咯并[1,2-a]喹喔啉通过转移氢化进行氧化动力学拆分相结合，整合为一锅法反应。该策略可同时高效合成多种光学活性的二氢吡咯并喹喔啉及二氢苯并噁嗪酮类化合物，且产率与对映体过量值俱佳。

值得注意的是，这一串联过程为合成具有强效农用杀菌活性的对映体富集二氢吡咯并[1,2-a]喹喔啉衍生物提供了直接有效的方法。该研究融合了受阻路易斯酸碱对催化的氢化反应与手性磷酸催化的转移氢化反应，为同步合成两类结构各异的光学活性含氮杂环化合物提供了一种简便高效的策略。

附：英文原文

Title: One-Pot Sequential Hydrogenation and Kinetic Resolution: Simultaneous Synthesis of Two Classes of Optically Active N-Heterocycles

Author: Zaiqi Han, Guangyu Cui, Xiangqing Feng, Haifeng Du

Issue&Volume: 2026-01-19

Abstract: Dihydropyrrolo[1,2-a]quinoxalines are important structural motifs widely present in natural products and biologically active molecules. Despite various well-developed racemic protocols, the enantioselective synthesis of optically active dihydropyrrolo[1,2-a]quinoxalines via asymmetric catalysis has been relatively less studied. In this work, a borane-catalyzed hydrogenation of pyrrolo[1,2-a]quinoxalines and a chiral phosphoric acid-catalyzed oxidative kinetic resolution of the resulting racemic dihydropyrrolo[1,2-a]quinoxalines via transfer hydrogenation have been successfully integrated into a one-pot process. A variety of optically active dihydropyrroquinoxalines and dihydrobenzoxazinones were obtained simultaneously with high levels of yields and ee's. Notably, this sequential process provides a straightforward method for synthesizing enantioenriched dihydropyrrolo[1,2-a]quinoxaline derivative, which acts as potent agricultural fungicides. The present work combines frustrated Lewis pair-catalyzed hydrogenation and chiral phosphoric acid-catalyzed transfer hydrogenation, providing a facile and efficient method for the simultaneous synthesis of two distinct classes of optically active nitrogen-containing heterocycles.

DOI: 10.1002/cjoc.70452

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70452