近日，南京大学俞寿云团队报道了光诱导钯催化实现动态动力学不对称烯丙基模拟。这一研究成果于2026年4月1日发表在《美国化学会志》上。

钯（Pd）催化的动态动力学不对称转化（DYKAT）为合成对映体富集分子提供了强有力的方法。尽管该策略在单取代和对称的1,3-二取代烯丙基底物中已得到充分发展，但对于非对称的1,3-二取代体系的DYKAT仍然是一个重大挑战，报道的通用解决方案很少。

研究组提出了一种光诱导钯催化的DYKAT方法，能够实现非对称1,3-二取代烯丙基亲电试剂（包括烯丙酯、乙烯基环氧化物和乙烯基碳酸酯）的高度区域选择性和对映选择性亚胺化。该方法可获得手性烯丙胺和氨基醇，区域选择性比高达>20:1，对映体过量值高达99%。机理研究表明，可见光激发促进了两种非对映的π-烯丙基钯(II)中间体的快速互变。这一过程涉及钯物种与烯丙基自由基之间的关键平衡，对于在温和条件下实现对映收敛转化至关重要。

附：英文原文

Title: Photoinduced Palladium Catalysis Enables Dynamic Kinetic Asymmetric Allylic Imidation

Author: Runquan Kang, Weiwei Jin, Xinru Zhang, Xian He, Xianli Yang, Xiang-Ai Yuan, Shouyun Yu

Issue&Volume: April 1, 2026

Abstract: Palladium (Pd)-catalyzed dynamic kinetic asymmetric transformation (DYKAT) provides a powerful approach to enantiomerically enriched molecules. Although well-established for monosubstituted and symmetric 1,3-disubstituted allylic substrates, the DYKAT of unsymmetrical 1,3-disubstituted systems remains a substantial challenge, with few general solutions reported. Here, we present a photoinduced Pd-catalyzed DYKAT that enables highly regio- and enantioselective imidation of unsymmetrical 1,3-disubstituted allylic electrophiles, including allyl esters, vinyl epoxides, and vinyl carbonates. This method delivers chiral allylamines and amino alcohols with up to >20:1 regioselectivity ratio and up to 99% enantiomeric excess. Mechanistic investigations reveal that visible-light excitation promotes rapid interconversion of two diastereomeric π-allyl Pd(II) intermediates. This process involves a key equilibrium between a Pd species and an allyl radical, which is essential for achieving enantioconvergent conversion under mild conditions.

DOI: 10.1021/jacs.5c17281

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c17281