Wolf Julian, Mohanan Meghana Poliyodath, Robidas Raphaël, Sutar Revannath L, Engelage Elric, Legault Claude Y, Huber Stefan M
Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
Department of Chemistry, Centre in Green Chemistry and Catalysis, Université de Sherbrooke, Sherbrooke, Québec, J1K 2R1, Canada.
Angew Chem Int Ed Engl. 2025 Jul 21;64(30):e202506476. doi: 10.1002/anie.202506476. Epub 2025 Jun 1.
As the employment of "non-classical" non-covalent interactions like halogen bonding (XB) in asymmetric catalysis is still at a very early stage, there are significant challenges to overcome. In some reported cases, the relevance of halogen bonding to the catalytic action is unclear, while in others, catalyst activity is limited. Herein, we present the second generation of a bidentate iodine(I)-based halogen bond donor as a modifiable and highly active chiral halogen bonding catalyst. With these modified derivatives, high stereocontrol of up to 98% ee could be achieved in a model Mukaiyama aldol reaction for a range of different substrates. Importantly, the crucial role of halogen bonding in this catalytic process was demonstrated by the low performance of the non-iodinated variants and by DFT calculations. The latter also indicate that the stereoinduction is based on the imposed orientation of the substrates towards each other.
由于在不对称催化中使用“非经典”非共价相互作用（如卤键（XB））仍处于非常早期的阶段，因此有重大挑战需要克服。在一些已报道的案例中，卤键与催化作用的相关性尚不清楚，而在其他案例中，催化剂活性有限。在此，我们展示了第二代基于双齿碘（I）的卤键供体，它是一种可修饰的高活性手性卤键催化剂。使用这些修饰的衍生物，在一系列不同底物的模型 Mukaiyama 羟醛反应中，可实现高达 98% ee 的高立体控制。重要的是，未碘化变体的低性能以及密度泛函理论（DFT）计算证明了卤键在该催化过程中的关键作用。DFT 计算还表明，立体诱导是基于底物相互之间的特定取向。
