| Autor: |
Hongliang Wang, Chengbu Liu, Dongju Zhang |
| Jazyk: |
angličtina |
| Rok vydání: |
2024 |
| Předmět: |
|
| Zdroj: |
Journal of CO2 Utilization, Vol 85, Iss , Pp 102874- (2024) |
| Druh dokumentu: |
article |
| ISSN: |
2212-9839 |
| DOI: |
10.1016/j.jcou.2024.102874 |
| Popis: |
DFT calculations on synthesis of benzothiazoles via cyclization of 2-aminothiophenols with CO2 and triethoxysilane have revealed a novel mechanism that fundamentally differs from previously proposed mechanisms. In this new mechanism, the acetate anion plays a pivotal role in both stages of the reaction: first, in the formation of the formoxysilane intermediate via CO2 reduction, and second, in its subsequent transformation to the product, benzothiazoles. The acetate anion acts as a nucleophile to activate the Si−H bond of triethoxysilane in the CO2 reduction stage and as a base, deprotonating 2-aminothiophenol and generating a HOAc molecule, which then acts as a proton shuttle in the subsequent transformations leading to the final product. Throughout the whole reaction process, it is the acetate anion that plays a substantial role in catalyzing the reaction by activating the Si–H bond of triethoxysilane, contrasting with the previous notion that the imidazolium cation activates CO2 through the formation of a NHC-CO2 adduct. Furthermore, the proposed mechanism offers a rational explanation for the observed inefficiency of imidazolium trifluoromethansulfonate as a catalyst for this reaction. The elucidation of this new mechanism sheds light on the intricate details of the benzothiazole synthesis and may inspire further investigations in this field. |
| Databáze: |
Directory of Open Access Journals |
| Externí odkaz: |
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Full Text from ScienceDirect