A Bifunctional Photoaminocatalyst for the Alkylation of Aldehydes: Design, Analysis, and Mechanistic Studies
[EN] A bifunctional photoaminocatalyst based on imidazolidinone and thioxanthone is presented. The preparation of these catalysts proceeds in a two-step synthesis that allows an easy tuning of the steric properties. The photophysical and electrochemical data of the imidazolidinone photocatalysts hav...
| Authors: | , , , , , , |
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| Format: | article |
| Publication Date: | 2018 |
| Country: | España |
| Institution: | Universitat Politècnica de València (UPV) |
| Repository: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Language: | English |
| OAI Identifier: | oai:riunet.upv.es:10251/192953 |
| Online Access: | https://riunet.upv.es/handle/10251/192953 |
| Access Level: | Open access |
| Keyword: | Bifunctional photocatalyst Organocatalysis Pyrrolidines Photochemistry Mechanism QUIMICA ORGANICA |
| Summary: | [EN] A bifunctional photoaminocatalyst based on imidazolidinone and thioxanthone is presented. The preparation of these catalysts proceeds in a two-step synthesis that allows an easy tuning of the steric properties. The photophysical and electrochemical data of the imidazolidinone photocatalysts have been determined, indicating that the catalysts can work under visible light conditions. To corroborate the experimental observations, ground state geometry optimization and energy transition studies of thioxanthone and bifunctional catalyst 4c were optimized by time-dependent density functional theory (TD DFT) calculations. The alkylation of aldehydes with this photoaminocatalyst works with high enantioselectivities and yields due to the stereoelectronic properties of the catalyst. A rational mechanistic cycle based on different mechanistic experiments, TD DFT calculations, and laser flash photolysis is presented. |
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