Sequential Metal-Free Thermal 1,3-Dipolar Cycloaddition of Unactivated Azomethine Ylides
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Title: | Sequential Metal-Free Thermal 1,3-Dipolar Cycloaddition of Unactivated Azomethine Ylides |
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Authors: | Selva, Verónica | Selva, Elisabet | Merino, Pedro | Nájera, Carmen | Sansano, Jose M. |
Research Group/s: | Síntesis Asimétrica (SINTAS) |
Center, Department or Service: | Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica |
Keywords: | Thermal 1,3-dipolar cycloaddition | Unactivated azomethine ylides | Sequential metal-free |
Knowledge Area: | Química Orgánica |
Issue Date: | 6-Jun-2018 |
Publisher: | American Chemical Society |
Citation: | Organic Letters. 2018, 20(12): 3522-3526. doi:10.1021/acs.orglett.8b01292 |
Abstract: | The thermal 1,3-dipolar cycloaddition of unactivated azomethine ylides derived from allylamine and aromatic or heteroaromatic aldehydes with maleimides and 1,1- and 1,2-bis(phenylsulfonyl)ethylene affords endo-2,5-trans cycloadducts in moderate to good yields. DFT calculations provide evidence that the diastereoselectivity observed depends on the isomerization between S- and W-ylides according to Curtin-Hammett’s principle. DFT calculations also explain the different diastereomeric ratio observed for 2-pyridyl and 2-thienyl derivatives in which the isomerization is not possible due to the competitiveness between isomerization barrier and the rate-limiting step (ylide formation barrier). This methodology is applied to the diastereoselective synthesis of a tricyclic thrombin inhibitor. |
Sponsor: | We gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (Project Nos. CTQ2013-43446-P, CTQ2014-51912-REDC, CTQ2016-76782-P, CTQ2016-81797-REDC, CTQ2016-81893REDT, and CTQ2016-76155-R), the Generalitat Valenciana (PROMETEOII/2014/017), the University of Alicante, and Medalchemy S. L. E.S. thanks University of Alicante and Medalchemy S. L. for a predoctoral fellowship. |
URI: | http://hdl.handle.net/10045/77171 |
ISSN: | 1523-7060 (Print) | 1523-7052 (Online) |
DOI: | 10.1021/acs.orglett.8b01292 |
Language: | eng |
Type: | info:eu-repo/semantics/article |
Rights: | © 2018 American Chemical Society |
Peer Review: | si |
Publisher version: | https://doi.org/10.1021/acs.orglett.8b01292 |
Appears in Collections: | INV - SINTAS - Artículos de Revistas |
Files in This Item:
File | Description | Size | Format | |
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2018_Selva_etal_OrgLett_final.pdf | Versión final (acceso restringido) | 1,08 MB | Adobe PDF | Open Request a copy |
2018_Selva_etal_OrgLett_revised.pdf | Versión revisada (acceso abierto) | 1,55 MB | Adobe PDF | Open Preview |
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