A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis-N-heterocycles: rationalization by electronic structure calculations
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Tartalom: http://real.mtak.hu/90215/
Archívum: REAL
Gyűjtemény: Status = Published
Subject = Q Science / természettudomány: QD Chemistry / kémia: QD03 Inorganic chemistry / szervetlen kémia
Type = Article
Cím:
A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis-N-heterocycles: rationalization by electronic structure calculations
Létrehozó:
Damas, Liliana
Carrilho, Rui M. B.
Nunes, Sandra C. C.
Pais, Alberto A. C. C.
Kollár, László
Pineiro, Marta
Pereira, Mariette M.
Kiadó:
Royal Society Publishing
Dátum:
2018-08-15
Téma:
QD03 Inorganic chemistry / szervetlen kémia
Tartalmi leírás:
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 (PCO ¼ 30 bar, T ¼ 808C, iodoindole/diamine ratio ¼ 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)-(þ)-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.
Nyelv:
magyar
Típus:
Article
PeerReviewed
info:eu-repo/semantics/article
Formátum:
text
Azonosító:
Damas, Liliana and Carrilho, Rui M. B. and Nunes, Sandra C. C. and Pais, Alberto A. C. C. and Kollár, László and Pineiro, Marta and Pereira, Mariette M. (2018) A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis-N-heterocycles: rationalization by electronic structure calculations. ROYAL SOCIETY OPEN SCIENCE, 5 (9). pp. 1-14. ISSN 2054-5703
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