Substituent effects on intramolecular Schmidt reactions: a theoretical study on the formation of bridged lactams.
| Autor: | Kosteczka GL; Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, PR, Brazil. renan@utfpr.edu.br., Soek RN; Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, PR, Brazil. renan@utfpr.edu.br., Richter WE; Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, PR, Brazil. renan@utfpr.edu.br., Campos RB; Universidade Tecnológica Federal do Paraná, Rua Deputado Heitor de Alencar Furtado, 5000, 81280-340, Curitiba, PR, Brazil. renan@utfpr.edu.br. |
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| Jazyk: | angličtina |
| Zdroj: | Organic & biomolecular chemistry [Org Biomol Chem] 2023 May 17; Vol. 21 (19), pp. 4114-4122. Date of Electronic Publication: 2023 May 17. |
| DOI: | 10.1039/d3ob00532a |
| Abstrakt: | The competitive formation of isomeric bridged lactams via acid-catalyzed intramolecular Schmidt reactions from 3-azidoethylcyclopentanones is explored using density functional theory (DFT) calculations, primarily performed at the M06-2X/6-311++G(d,p) level of theory. The results indicate that specific substituents installed at α-carbons can efficiently control the regioselectivity of the reaction by lone pair-cation interactions or steric hindrance reversing the main product preference, whereas cation-π interactions are not so effective. |
| Databáze: | MEDLINE |
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