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Title: A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis-N-heterocycles: rationalization by electronic structure calculations
Authors: Damas, Liliana Reis 
Carrilho, Rui M. B. 
Nunes, Sandra 
Pais, Alberto 
Kollár, László 
Pineiro, Marta 
Pereira, Mariette M. 
Keywords: carbonylation; cyclization; indole; palladium; tandem reactions
Issue Date: Sep-2018
Publisher: The Royal Society
Project: PEst-OE/QUI/UI0313/2014 
P-2.3.2-15-2016-00049 and K113177 
Serial title, monograph or event: Royal Society Open Science
Volume: 5
Issue: 9
Abstract: An unprecedented palladium-catalysed sequential aminocarbonylation/cyclization synthetic strategy, using carbon monoxide and structurally different aliphatic diamines as N-nucleophiles, gives access, in one pot, to a new family of indole-based N-heterocyclic derivatives (hydropyrazinones, benzodiazepinones and hydroquinoxalines). Optimization of the reaction conditions towards double carbonylation (P CO = 30 bar, T = 80°C, iodoindole/diamine ratio = 1 : 1.5, toluene as solvent) allowed the target cyclic products, which are formed in situ via intramolecular cyclization of the ketocarboxamide intermediates, to be obtained through a nucleophilic addition/elimination reaction with the pendant terminal amine groups. The structure of the diamine nucleophile was revealed to affect the reaction's selectivity, with the best yields for the cyclic products being obtained in the presence of (1S,2S)-(+)-cyclohexane-1,2-diamine (a) as the nucleophile, using either 5- or 7-iodoindole as the substrate. The reaction's selectivity was rationalized based on electronic structure calculations, which explain the effect of the diamine structure on the predominant formation of the cyclic products.
ISSN: 2054-5703
DOI: 10.1098/rsos.181140
Rights: openAccess
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais

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