Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/108032
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 UID/QUI/00313/2013 PD/BD/106020/2014 SFRH/BPD/100537/2014 SFRH/BPD/71683/2010. POCI-01-0145-FEDER-016387 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. | URI: | https://hdl.handle.net/10316/108032 | ISSN: | 2054-5703 | DOI: | 10.1098/rsos.181140 | Rights: | openAccess |
Appears in Collections: | I&D CQC - Artigos em Revistas Internacionais |
Files in This Item:
Page view(s)
83
checked on Oct 9, 2024
Download(s)
51
checked on Oct 9, 2024
Google ScholarTM
Check
Altmetric
Altmetric
This item is licensed under a Creative Commons License