Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles
A general Rh-catalyzed addition reaction of nitrogen containing heterocycles to internal allenes is reported. Starting from racemic internal allenes a dynamic kinetic resolution (DKR) provides <i>N</i>-allylated triazoles and tetrazoles. Simultaneous control of <i>N</i><su...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-10-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/12/10/1209 |
| _version_ | 1797474453399011328 |
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| author | Simon V. Sieger Ilja Lubins Bernhard Breit |
| author_facet | Simon V. Sieger Ilja Lubins Bernhard Breit |
| author_sort | Simon V. Sieger |
| collection | DOAJ |
| description | A general Rh-catalyzed addition reaction of nitrogen containing heterocycles to internal allenes is reported. Starting from racemic internal allenes a dynamic kinetic resolution (DKR) provides <i>N</i>-allylated triazoles and tetrazoles. Simultaneous control of <i>N</i><sup>1</sup>/<i>N</i><sup>x</sup>-position selectivity, enantioselectivity and olefin geometry gives access to important building blocks of target-oriented synthesis. The synthetic utility is demonstrated by a gram-scale reaction and a broad substrate scope tolerating multiple functional groups. Deuterium labeling experiments and experiments with enantioenriched allenes as starting material support a plausible reaction mechanism. |
| first_indexed | 2024-03-09T20:30:18Z |
| format | Article |
| id | doaj.art-9bcdb355f6bf45509644c28e9275c422 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-09T20:30:18Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-9bcdb355f6bf45509644c28e9275c4222023-11-23T23:25:27ZengMDPI AGCatalysts2073-43442022-10-011210120910.3390/catal12101209Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and TetrazolesSimon V. Sieger0Ilja Lubins1Bernhard Breit2Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstraße 21, 79104 Freiburg im Breisgau, GermanyInstitut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstraße 21, 79104 Freiburg im Breisgau, GermanyInstitut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstraße 21, 79104 Freiburg im Breisgau, GermanyA general Rh-catalyzed addition reaction of nitrogen containing heterocycles to internal allenes is reported. Starting from racemic internal allenes a dynamic kinetic resolution (DKR) provides <i>N</i>-allylated triazoles and tetrazoles. Simultaneous control of <i>N</i><sup>1</sup>/<i>N</i><sup>x</sup>-position selectivity, enantioselectivity and olefin geometry gives access to important building blocks of target-oriented synthesis. The synthetic utility is demonstrated by a gram-scale reaction and a broad substrate scope tolerating multiple functional groups. Deuterium labeling experiments and experiments with enantioenriched allenes as starting material support a plausible reaction mechanism.https://www.mdpi.com/2073-4344/12/10/1209asymmetric catalysisdynamic kinetic resolutioninternal allenesrhodiumhydroamination |
| spellingShingle | Simon V. Sieger Ilja Lubins Bernhard Breit Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles Catalysts asymmetric catalysis dynamic kinetic resolution internal allenes rhodium hydroamination |
| title | Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles |
| title_full | Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles |
| title_fullStr | Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles |
| title_full_unstemmed | Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles |
| title_short | Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes towards Chiral Allylated Triazoles and Tetrazoles |
| title_sort | rhodium catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles |
| topic | asymmetric catalysis dynamic kinetic resolution internal allenes rhodium hydroamination |
| url | https://www.mdpi.com/2073-4344/12/10/1209 |
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