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
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

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