郑州大学梅光建/贾世琨ACS Catal.:双核锌催化消旋2H-azirines的形式平行动力学拆分不对称合成手性氮杂环丙烷醇
图1. TOC (图片来源于ACS Catal.)We present a parallel kinetic resolution (PKR) of racemic 2H-azirines via zinc-catalyzed direct nucleophilic additions to the C=N double bonds with 2-hydroxyacetophenones. Two sets of separable diastereomers of chiral aziridine alcohols bearing three adjacent stereocenters are prepared with high enantioselectivity. Diastereodivergent synthesis of four stereoisomers is realized by switching the absolute configurations of the chiral ligand. Control experiments and DFT calculations are carried out to shed light on the stereochemical models during the PKR progress.图2. 研究背景及本策略 (图片来源于ACS Catal.)图3. 条件优化 (图片来源于ACS Catal.)图4. 2-羟基苯乙酮底物范围 (图片来源于ACS Catal.)图5. 2H-azirines底物范围 (图片来源于ACS Catal.)图6. 非对映发散性合成、放大反应、衍生化及合成应用 (图片来源于ACS Catal.)图7. 控制实验、非线性效应研究及反应过程监测 (图片来源于ACS Catal.)图8. DFT计算 (图片来源于ACS Catal.)图9. 过渡态中弱相互作用影响反应 (图片来源于ACS Catal.)In summary, we have applied the dinuclear zinc cooperative catalyst for the formal PKR of racemic 2H-azirines. With this new protocol, two sets of chiral aziridine alcohols bearing three adjacent stereocenters were furnished in high levels of stereocontrol. The derivatizations of products and diastereodivergent synthesis as well as preliminary application as a chiral ligand exhibited the potential utility of our method. Control experiments and nonlinear effects studies were performed to understand stereochemical models of this transformation. The DFT calculations shed light on the origin of the enantioselectivity of the reaction and further explorations of these PKRs are ongoing in our laboratory.
