强氢键供体溶剂加速帕瑟里尼三组分反应。
Strong Hydrogen Bond Donating Solvents Accelerate the Passerini Three-Component Reaction.
作者信息
Ferdeghini Claudio, Wu Minghui, Ranjan Prabhat, Würdemann Martien A, Pyschik Jan, Mitsos Alexander, Ruijter Eelco, Orru Romano V A, Hansen Thomas, Saya Jordy M
机构信息
Biobased Organic Chemistry, Aachen-Maastricht Institute for Biobased Materials (AMIBM), Maastricht University, Urmonderbaan 22, Geleen 6167RD, The Netherlands.
Process Systems Engineering, RWTH Aachen University, Schinkelstrasse 8, Aachen 52062, Germany.
出版信息
J Org Chem. 2025 Apr 11;90(14):5000-5007. doi: 10.1021/acs.joc.5c00236. Epub 2025 Apr 3.
We report enhanced reaction rates of the Passerini reaction (P-3CR) using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as a cosolvent. Although alcoholic solvents typically increase the energy barrier of the rate-determining step for the P-3CR, we observed significant rate enhancements even when employing strong hydrogen bond donating (HBD) alcohols as cosolvents. This rate enhancement was observed for most aprotic organic solvents, with the exception of strong hydrogen bond accepting (HBA) solvents such as DMF. Experimental kinetic studies and DFT calculations provided a mechanistic rationale for our observations. An investigation of the substrate scope showed that this rate enhancement generally resulted in a (slight) increase of the overall yield in the P-3CR.
我们报道了使用1,1,1,3,3,3-六氟异丙醇（HFIP）作为共溶剂时，Passerini反应（P-3CR）的反应速率得到了提高。尽管醇类溶剂通常会增加P-3CR速率决定步骤的能垒，但我们发现，即使使用强氢键供体（HBD）醇类作为共溶剂，反应速率也有显著提高。除了强氢键受体（HBA）溶剂（如DMF）外，在大多数非质子有机溶剂中都观察到了这种速率提高。实验动力学研究和密度泛函理论（DFT）计算为我们的观察结果提供了机理依据。对底物范围的研究表明，这种速率提高通常会使P-3CR的总产率（略有）增加。
Zotero 插件