近日，美国威斯康星大学麦迪逊分校Tehshik P. Yoon团队报道了基于优势吡啶双噁唑啉骨架的模块化对映选择性光催化剂。2026年4月9日出版的《科学》杂志发表了这项成果。

现代有机合成依赖于手性催化剂的可及性，以控制成键反应的立体化学。几类手性催化剂已被公认为“优势”结构，因为它们在涉及不同反应机理的多种转化中具有显著的通用性。然而，高对映选择性光催化剂结构的例子仍然很少。

研究组通过将具有给电子性质的咔唑单元修饰到优势的吡啶双噁唑啉配合物结构中，设计了一类对映选择性光催化剂。这些手性配体可从商业可得的手性原料出发，经三步合成序列获得，并且其电荷转移光化学性质可被合理调控，以优化光催化活性。我们通过三个模型不对称反应（包括光氧化还原反应和激发态光反应）验证了这类新型手性光催化剂结构的通用性。

附：英文原文

Title: Modular enantioselective photocatalysts from privileged pybox scaffolds

Author: Riley M. Kelch, Lea Hmmerling, Eli Zysman-Colman, Tehshik P. Yoon

Issue&Volume: 2026-04-09

Abstract: Modern organic synthesis relies upon the availability of chiral catalysts to control the stereochemistry of bond-forming reactions. Several families of chiral catalysts have become recognized as “privileged” structures because of their notable generality for diverse transformations with different reaction mechanisms. However, examples of highly enantioselective photocatalyst structures remain scarce. We have designed a family of enantioselective photocatalysts by modifying the structures of privileged pyridine bis(oxazoline) complexes with electron-donating carbazole units. The chiral ligands are accessible through a three-step synthetic sequence starting from commercially available chiral pool materials, and their charge-transfer photochemistry can be rationally tuned to optimize photocatalytic activity. We demonstrate the generality of these new chiral photocatalyst structures in a series of three model asymmetric reactions, which includes both photoredox and excited-state photoreactions.

DOI: aeb5832

Source: https://www.science.org/doi/10.1126/science.aeb5832