Deacylative Reactions: Synthetic Applications

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Title: Deacylative Reactions: Synthetic Applications
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.
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
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Appears in Collections:INV - SINTAS - Artículos de Revistas

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