A novel Pd-catalysed sequential carbonylation/cyclization approach toward bis-N-heterocycles: Rationalization by electronic structure calculations

8Citations
Citations of this article
12Readers
Mendeley users who have this article in their library.

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 (PCO = 30 bar, T = 808C, 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.

References Powered by Scopus

General atomic and molecular electronic structure system

20190Citations
N/AReaders
Get full text

Synthesis of heterocycles via palladium-catalyzed carbonylations

1145Citations
N/AReaders
Get full text

Biomedical importance of indoles

1080Citations
N/AReaders
Get full text

Cited by Powered by Scopus

Double Carbonylation Reactions: Overview and Recent Advances

49Citations
N/AReaders
Get full text

Rhodium-Catalyzed C(sp<sup>2</sup>)-H Alkoxycarbonylation/Acylation of Indolines with Anhydrides as a Carbonyl Source

19Citations
N/AReaders
Get full text

Carbon Monoxide as C1 Building Block in Fine Chemical Synthesis<sup>†</sup>

15Citations
N/AReaders
Get full text

Register to see more suggestions

Mendeley helps you to discover research relevant for your work.

Already have an account?

Cite

CITATION STYLE

APA

Damas, L., Carrilho, R. M. B., Nunes, S. C. C., Pais, A. A. C. C., Kollár, L., Pineiro, M., & Pereira, M. 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). https://doi.org/10.1098/rsos.181140

Readers' Seniority

Tooltip

Professor / Associate Prof. 3

38%

Researcher 3

38%

PhD / Post grad / Masters / Doc 2

25%

Readers' Discipline

Tooltip

Chemistry 6

75%

Biochemistry, Genetics and Molecular Bi... 1

13%

Engineering 1

13%

Save time finding and organizing research with Mendeley

Sign up for free