Palladium-catalyzed allylation and deacylative allylation of 3-acetyl-2-oxindoles with allylic alcohols
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Title: | Palladium-catalyzed allylation and deacylative allylation of 3-acetyl-2-oxindoles with allylic alcohols |
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Authors: | Ortega-Martínez, Aitor | Lorenzo, Rocco de | Sansano, Jose M. | Nájera, Carmen |
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: | Oxindoles | Allylic alcohols | Palladium | Catalysis | Deacylation |
Knowledge Area: | Química Orgánica |
Issue Date: | 11-Jan-2018 |
Publisher: | Elsevier |
Citation: | Tetrahedron. 2018, 74(2): 253-259. doi:10.1016/j.tet.2017.11.041 |
Abstract: | The Pd-catalyzed allylation of 3-acetyl-2-oxindoles with allyl alcohol is performed using 3 mol% of Pd(dba)2, rac-BINAP and BINOL phosphoric acid as catalytic mixture. This procedure allows the in situ synthesis of 3-allyl-2-oxindole by adding Triton B to the reaction mixture. The deacylative allylation of 3-acetyl-3-methyl-2-oxindoles with allylic alcohols is carried out with 3 mol% of Pd(OAc)2, dppp and 1.5 equiv. of LiOtBu as base affording the corresponding 3,3-disubstituted 2-oxindoles in good yields. Both methodologies can be combined for the preparation of unsymmetrical 3,3-diallylated 2-oxindoles such as compound 7. The DaA must be carried out in the absence of oxygen in order to avoid the competitive formation of 3-alkyl-3-hydroxy-2-indoles. The later compounds can be easily obtained by deacylative oxidation of 3-alkylated 3-acetyl-2-oxindoles with LiOEt at rt under air. |
Sponsor: | We gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO2009/039 and PROMETEOII/2014/017) and the University of Alicante. A. O.-M. thanks MINECO for a predoctoral fellowship. |
URI: | http://hdl.handle.net/10045/72136 |
ISSN: | 0040-4020 (Print) | 1464-5416 (Online) |
DOI: | 10.1016/j.tet.2017.11.041 |
Language: | eng |
Type: | info:eu-repo/semantics/article |
Rights: | © 2017 Elsevier Ltd. |
Peer Review: | si |
Publisher version: | http://dx.doi.org/10.1016/j.tet.2017.11.041 |
Appears in Collections: | INV - SINTAS - Artículos de Revistas |
Files in This Item:
File | Description | Size | Format | |
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2018_Ortega-Martinez_etal_Tetrahedron_final.pdf | Versión final (acceso restringido) | 1,07 MB | Adobe PDF | Open Request a copy |
2018_Ortega-Martinez_etal_Tetrahedron_accepted.pdf | Accepted Manuscript (acceso abierto) | 1,54 MB | Adobe PDF | Open Preview |
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