Masuda Koichiro, Kobayashi Shū
Department of Chemistry, School of Science, The University of Tokyo. Hongo Bunkyo-ku Tokyo 113-0033 Japan
Chem Sci. 2020 Apr 14;11(19):5105-5112. doi: 10.1039/d0sc00021c.
This new method overcomes problems of conventional analytical methodologies such as light scattering and sampling reproducibility issues. We used this method for mechanistic studies of catalytic reactions under heterogeneous conditions. Direct-type hydroxymethylation reactions and Mukaiyama-type hydroxymethylation reactions both catalyzed by a scandium-bipyridine ligand complex under micellar conditions were employed as examples of heterogeneous reactions. For direct-type hydroxymethylation reactions, initial reaction rate assays revealed first-order dependency on both substrate and catalyst. On the other hand, Mukaiyama-type hydroxymethylation reactions showed first-order rate dependency on substrate, zero-order on catalyst and saturation kinetics on formaldehyde.
这种新方法克服了传统分析方法存在的问题,如光散射和采样重现性问题。我们将此方法用于多相条件下催化反应的机理研究。以在胶束条件下由钪-联吡啶配体络合物催化的直接型羟甲基化反应和 Mukaiyama 型羟甲基化反应作为多相反应的实例。对于直接型羟甲基化反应,初始反应速率测定表明对底物和催化剂均呈一级依赖性。另一方面,Mukaiyama 型羟甲基化反应对底物呈一级速率依赖性,对催化剂呈零级依赖性,对甲醛呈饱和动力学。