Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement
The first catalytic enantioselective pinacol rearrangement was reported by Antilla and co-workers in 2010. The reaction was catalyzed by a chiral phosphoric acid and resulted in high levels of enantioselectivity (up to 96% ee). The present study uses density functional theory to investigate the mech...
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2018
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v83_n23_p14683_Falcone http://hdl.handle.net/20.500.12110/paper_00223263_v83_n23_p14683_Falcone |
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paper:paper_00223263_v83_n23_p14683_Falcone2023-06-08T14:49:39Z Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement Catalysis Catalyst selectivity Cyclization Density functional theory Hydrogen bonds Phosphoric acid Enantioselective Phosphate group Pinacol rearrangements Transition state Enantioselectivity alcohol indole phosphate phosphoric acid Article asymmetric catalysis chirality conformation density functional theory enantioselectivity hydrogen bond molecular dynamics pinacol rearrangement reaction analysis stereoselectivity The first catalytic enantioselective pinacol rearrangement was reported by Antilla and co-workers in 2010. The reaction was catalyzed by a chiral phosphoric acid and resulted in high levels of enantioselectivity (up to 96% ee). The present study uses density functional theory to investigate the mechanism and origins of stereoselectivity of this important reaction and to explain the difference in selectivity between different catalysts. An OH···O hydrogen bond between the intermediate indolyl alcohol and the phosphate group from the catalyst together with a CH···O hydrogen bond between the indole and the phosphate group were observed in the preferred activation mode for the stereodetermining [1,2]-aryl shift. A stronger CH···O interaction in the major transition state was found to contribute to the high levels of enantioselectivity. A more bulky catalyst (TRIP) was found to impede the formation of the key CH···O interaction, leading to lower levels of enantioselectivity. © 2018 American Chemical Society. 2018 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v83_n23_p14683_Falcone http://hdl.handle.net/20.500.12110/paper_00223263_v83_n23_p14683_Falcone |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Catalysis Catalyst selectivity Cyclization Density functional theory Hydrogen bonds Phosphoric acid Enantioselective Phosphate group Pinacol rearrangements Transition state Enantioselectivity alcohol indole phosphate phosphoric acid Article asymmetric catalysis chirality conformation density functional theory enantioselectivity hydrogen bond molecular dynamics pinacol rearrangement reaction analysis stereoselectivity |
| spellingShingle |
Catalysis Catalyst selectivity Cyclization Density functional theory Hydrogen bonds Phosphoric acid Enantioselective Phosphate group Pinacol rearrangements Transition state Enantioselectivity alcohol indole phosphate phosphoric acid Article asymmetric catalysis chirality conformation density functional theory enantioselectivity hydrogen bond molecular dynamics pinacol rearrangement reaction analysis stereoselectivity Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| topic_facet |
Catalysis Catalyst selectivity Cyclization Density functional theory Hydrogen bonds Phosphoric acid Enantioselective Phosphate group Pinacol rearrangements Transition state Enantioselectivity alcohol indole phosphate phosphoric acid Article asymmetric catalysis chirality conformation density functional theory enantioselectivity hydrogen bond molecular dynamics pinacol rearrangement reaction analysis stereoselectivity |
| description |
The first catalytic enantioselective pinacol rearrangement was reported by Antilla and co-workers in 2010. The reaction was catalyzed by a chiral phosphoric acid and resulted in high levels of enantioselectivity (up to 96% ee). The present study uses density functional theory to investigate the mechanism and origins of stereoselectivity of this important reaction and to explain the difference in selectivity between different catalysts. An OH···O hydrogen bond between the intermediate indolyl alcohol and the phosphate group from the catalyst together with a CH···O hydrogen bond between the indole and the phosphate group were observed in the preferred activation mode for the stereodetermining [1,2]-aryl shift. A stronger CH···O interaction in the major transition state was found to contribute to the high levels of enantioselectivity. A more bulky catalyst (TRIP) was found to impede the formation of the key CH···O interaction, leading to lower levels of enantioselectivity. © 2018 American Chemical Society. |
| title |
Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| title_short |
Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| title_full |
Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| title_fullStr |
Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| title_full_unstemmed |
Mechanistic Insights into a Chiral Phosphoric Acid-Catalyzed Asymmetric Pinacol Rearrangement |
| title_sort |
mechanistic insights into a chiral phosphoric acid-catalyzed asymmetric pinacol rearrangement |
| publishDate |
2018 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v83_n23_p14683_Falcone http://hdl.handle.net/20.500.12110/paper_00223263_v83_n23_p14683_Falcone |
| _version_ |
1768544307542753280 |