Niwayama Satomi, Hiraga Yoshikazu
Graduate School of Engineering, Muroran Institute of Technology, Muroran, Hokkaido 050-8585, Japan.
Department of Food Sciences and Biotechnology, Hiroshima Institute of Technology, Hiroshima 731-5193, Japan.
ACS Omega. 2023 Sep 5;8(37):33819-33824. doi: 10.1021/acsomega.3c04318. eCollection 2023 Sep 19.
Water-mediated organic reactions significantly contribute to the protection of the environment. Desymmetrization reactions, which convert only one of the identical functional groups within one molecule, are cost-effective because of the low cost of the starting materials. In combination with these two merits, highly efficient and practical selective monohydrolysis reactions of symmetric diesters were previously reported. The products of these reactions are versatile building blocks. The mechanisms of this reaction are hypothesized to proceed through micellar aggregates in which the hydrophilic carboxylate anions formed by monohydrolysis are directed outward and the remaining hydrophobic groups are directed inward in governing the selectivities. Here, dynamic light scattering and electrophoretic light scattering experiments were performed for detection of the key intermediates in the reaction. These experiments revealed the existence of aggregates with negative charges on the surface in the mainly aqueous media, supporting the reaction mechanisms that control the high selectivities.
水介导的有机反应对环境保护有显著贡献。去对称化反应仅转化分子内一个相同的官能团，由于起始原料成本低，因而具有成本效益。结合这两个优点，之前曾报道过对称二酯的高效且实用的选择性单水解反应。这些反应的产物是通用的结构单元。据推测，该反应的机理是通过胶束聚集体进行的，其中单水解形成的亲水性羧酸根阴离子向外定向，而其余疏水性基团向内定向，从而控制选择性。在此，进行了动态光散射和电泳光散射实验以检测反应中的关键中间体。这些实验揭示了在主要为水性的介质中存在表面带负电荷的聚集体，这支持了控制高选择性的反应机理。
