Deacylative Reactions: Synthetic Applications
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Title: | Deacylative Reactions: Synthetic Applications |
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Authors: | Ortega-Martínez, Aitor | Molina, Cynthia | Moreno-Cabrerizo, Cristina | 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: | Enolates | Alkylation | Palladium | Homogeneous catalysis | Allylic alcohols | Fluorine |
Knowledge Area: | Química Orgánica |
Issue Date: | 7-Jun-2018 |
Publisher: | Wiley-VCH Verlag GmbH & Co. KGaA |
Citation: | European Journal of Organic Chemistry. 2018, 20-21: 2394-2405. doi:10.1002/ejoc.201800063 |
Abstract: | Herein we introduce the recent developments of a new strategy based on deacylative alkylation (DaA) reactions for the generation of quaternary stereocenters based on the in situ preparation and functionalization of enolates under very mild reaction conditions. Palladium‐catalyzed deacylative allylation and benzylation reactions of carbon nucleophiles are performed with the corresponding alcohols. This methodology has been applied to the synthesis of the calcium ion channel blocker verapamil, the antiviral (+)‐hamigeran B, several oxindole precursors of esermethole, horsfiline, physostigmine, phenserine, meso‐folicanthine, meso‐chinonanthine and the dimer cyclotriptamine alkaloids. Base‐promoted deacylative reactions enable the functionalization of 2‐oxindole enolates at the 3‐position with alkyl halides and electrophilic alkenes. In the presence of oxygen or air, 3‐hydroxy‐2‐oxindoles are prepared by deacylative oxidation. Detrifluoroacylative reactions are promoted by a base generating fluoroenolates, which can participate in aldol, Mannich and Michael reactions for the preparation of important fluorinated intermediates. Finally, palladium‐catalyzed deacylative cross‐coupling of acetyl diazoacetates and phosphonates with aryl iodides let to the formation of aryl diazoacetates and phosphonates, respectively. The same process, with 2‐iodoazoarenes and 2‐iodoaryltriazenes, gives 2H‐indazoles, which are important pharmacophores. |
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 (PROMETEOII/2014/017), and the University of Alicante. A. O.-M. thanks MINECO for a predoctoral fellowship. |
URI: | http://hdl.handle.net/10045/76191 |
ISSN: | 1434-193X (Print) | 1099-0690 (Online) |
DOI: | 10.1002/ejoc.201800063 |
Language: | eng |
Type: | info:eu-repo/semantics/article |
Rights: | © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim |
Peer Review: | si |
Publisher version: | https://doi.org/10.1002/ejoc.201800063 |
Appears in Collections: | INV - SINTAS - Artículos de Revistas |
Files in This Item:
File | Description | Size | Format | |
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2018_Ortega-Martinez_etal_EurJOrgChem_final.pdf | Versión final (acceso restringido) | 2,21 MB | Adobe PDF | Open Request a copy |
2018_Ortega-Martinez_etal_EurJOrgChem_accepted.pdf | Accepted Manuscript (acceso abierto) | 2,38 MB | Adobe PDF | Open Preview |
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