Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams
We explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of <i>N</i>-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of e...
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| Format: | Article |
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MDPI AG
2023-08-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/13/9/1258 |
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| author | Alexander Q. Cusumano Tianyi Zhang William A. Goddard Brian M. Stoltz |
| author_facet | Alexander Q. Cusumano Tianyi Zhang William A. Goddard Brian M. Stoltz |
| author_sort | Alexander Q. Cusumano |
| collection | DOAJ |
| description | We explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of <i>N</i>-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of experimental results. Ultimately, we propose that the enhancement in enantioselectivity arises primarily from noncovalent interactions between the substrate and ligand rather than secondary substrate chelation, as previously hypothesized. |
| first_indexed | 2024-03-10T22:56:22Z |
| format | Article |
| id | doaj.art-82f1e14634ab4afa86871ee073d67f7d |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T22:56:22Z |
| publishDate | 2023-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-82f1e14634ab4afa86871ee073d67f7d2023-11-19T09:57:56ZengMDPI AGCatalysts2073-43442023-08-01139125810.3390/catal13091258Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl LactamsAlexander Q. Cusumano0Tianyi Zhang1William A. Goddard2Brian M. Stoltz3The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USAThe Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USAMaterials and Process Simulation Center, Beckman Institute, California Institute of Technology, Pasadena, CA 91125, USAThe Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USAWe explore the origins of the marked improvement in enantioselectivity in the inner-sphere (PHOX)Pd-catalyzed allylic alkylation of <i>N</i>-benzoyl lactam nucleophiles over their carbocyclic counterparts. We employ density functional theory calculations to aid in the interpretation of experimental results. Ultimately, we propose that the enhancement in enantioselectivity arises primarily from noncovalent interactions between the substrate and ligand rather than secondary substrate chelation, as previously hypothesized.https://www.mdpi.com/2073-4344/13/9/1258C(sp<sup>3</sup>)–C(sp<sup>3</sup>) cross-couplingasymmetric catalysiscomputationallylic alkylation |
| spellingShingle | Alexander Q. Cusumano Tianyi Zhang William A. Goddard Brian M. Stoltz Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams Catalysts C(sp<sup>3</sup>)–C(sp<sup>3</sup>) cross-coupling asymmetric catalysis computation allylic alkylation |
| title | Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams |
| title_full | Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams |
| title_fullStr | Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams |
| title_full_unstemmed | Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams |
| title_short | Origins of Enhanced Enantioselectivity in the Pd-Catalyzed Decarboxylative Allylic Alkylation of <em>N</em>-Benzoyl Lactams |
| title_sort | origins of enhanced enantioselectivity in the pd catalyzed decarboxylative allylic alkylation of em n em benzoyl lactams |
| topic | C(sp<sup>3</sup>)–C(sp<sup>3</sup>) cross-coupling asymmetric catalysis computation allylic alkylation |
| url | https://www.mdpi.com/2073-4344/13/9/1258 |
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