Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline
Prolinamides are well-known organocatalysts for the HSiCl<sub>3</sub> reduction of imines; however, custom design of catalysts is based on trial-and-error experiments. In this work, we have used a combination of computational calculations and experimental work, including kinetic analyses...
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| Autores principales: | , , , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/a52609bd5e3c495d9e16c28d8b361915 |
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| Sumario: | Prolinamides are well-known organocatalysts for the HSiCl<sub>3</sub> reduction of imines; however, custom design of catalysts is based on trial-and-error experiments. In this work, we have used a combination of computational calculations and experimental work, including kinetic analyses, to properly understand this process and to design optimized catalysts for the benchmark (E)-<i>N</i>-(1-phenylethylidene)aniline. The best results have been obtained with the amide derived from 4-methoxyaniline and the <i>N</i>-pivaloyl protected proline, for which the catalyzed process is almost 600 times faster than the uncatalyzed one. Mechanistic studies reveal that the formation of the component supramolecular complex catalyst-HSiCl<sub>3</sub>-substrate, involving hydrogen bonding breaking and costly conformational changes in the prolinamide, is an important step in the overall process. |
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