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...
Guardado en:
| Autores principales: | , , , , , |
|---|---|
| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
|
| Materias: | |
| Acceso en línea: | https://doaj.org/article/a52609bd5e3c495d9e16c28d8b361915 |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| id |
oai:doaj.org-article:a52609bd5e3c495d9e16c28d8b361915 |
|---|---|
| record_format |
dspace |
| spelling |
oai:doaj.org-article:a52609bd5e3c495d9e16c28d8b3619152021-11-25T18:28:45ZRational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline10.3390/molecules262269631420-3049https://doaj.org/article/a52609bd5e3c495d9e16c28d8b3619152021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/22/6963https://doaj.org/toc/1420-3049Prolinamides 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.María MaciáRaúl PorcarVicente Martí-CentellesEduardo García-VerdugoMaria Isabel BurgueteSantiago V. LuisMDPI AGarticleorganocatalysisasymmetric catalysistrichlorosilaneimine reductionmechanistic studiesOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6963, p 6963 (2021) |
| institution |
DOAJ |
| collection |
DOAJ |
| language |
EN |
| topic |
organocatalysis asymmetric catalysis trichlorosilane imine reduction mechanistic studies Organic chemistry QD241-441 |
| spellingShingle |
organocatalysis asymmetric catalysis trichlorosilane imine reduction mechanistic studies Organic chemistry QD241-441 María Maciá Raúl Porcar Vicente Martí-Centelles Eduardo García-Verdugo Maria Isabel Burguete Santiago V. Luis Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| description |
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. |
| format |
article |
| author |
María Maciá Raúl Porcar Vicente Martí-Centelles Eduardo García-Verdugo Maria Isabel Burguete Santiago V. Luis |
| author_facet |
María Maciá Raúl Porcar Vicente Martí-Centelles Eduardo García-Verdugo Maria Isabel Burguete Santiago V. Luis |
| author_sort |
María Maciá |
| title |
Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| title_short |
Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| title_full |
Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| title_fullStr |
Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| title_full_unstemmed |
Rational Design of Simple Organocatalysts for the HSiCl<sub>3</sub> Enantioselective Reduction of (E)-<i>N</i>-(1-Phenylethylidene)aniline |
| title_sort |
rational design of simple organocatalysts for the hsicl<sub>3</sub> enantioselective reduction of (e)-<i>n</i>-(1-phenylethylidene)aniline |
| publisher |
MDPI AG |
| publishDate |
2021 |
| url |
https://doaj.org/article/a52609bd5e3c495d9e16c28d8b361915 |
| work_keys_str_mv |
AT mariamacia rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline AT raulporcar rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline AT vicentemarticentelles rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline AT eduardogarciaverdugo rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline AT mariaisabelburguete rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline AT santiagovluis rationaldesignofsimpleorganocatalystsforthehsiclsub3subenantioselectivereductionofeini1phenylethylideneaniline |
| _version_ |
1718411096597987328 |