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
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.
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
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Appears in Collections:INV - SINTAS - Artículos de Revistas

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