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Current Organic Chemistry

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ISSN (Print): 1385-2728
ISSN (Online): 1875-5348

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Research Article

New Trends in 1,4-Dipolar Cycloaddition Reactions. Thermodynamic Control Synthesis of Model 2'-(isoquinolin-1-yl)-spiro[oxindole-3,3'-pyrrolines]

Author(s): Areej M. Jaber, Jalal A. Zahra*, Salim S. Sabri, Monther A. Khanfar, Firas F. Awwadi and Mustafa M. El-Abadelah*

Volume 26, Issue 5, 2022

Published on: 05 April, 2022

Page: [542 - 549] Pages: 8

DOI: 10.2174/1385272826666220221141306

Price: $65

Abstract

Background: A direct synthesis of functionalized spiro[oxindole-3,3'-pyrrolines] is achieved via thermodynamic control (~60 oC), three-component 1,4-dipolar cycloaddition reaction involving 3-phenylimidazo[5,1-a]isoquinoline, dimethyl acetylenedicarboxylate, and N-alkylisatins.

Methods: Conversely, this one-pot reaction furnished, upon conduction at 25-38 oC, the expected 1,3-oxazepino[7,6-b]indoles as the main kinetic control products. The calculated energy of the optimized molecular structures of model spiro-oxindole and its isomeric oxazepinoindole indicate that spiro-oxindole is more stable by 76.1 kJ/mol.

Results: The structures of the synthesized spiro adducts were evidenced from NMR and MS spectral data and further confirmed by single-crystal X-ray diffraction. Characteristic features of the spiro-oxindoles are displaced in their 13C-spectra as diagnostic signals at ~53 and ~70 ppm assigned, respectively, to the spiro carbon-3 and sp3 CH-2' of the pyrroline ring.

Conclusion: This unprecedented thermally induced pathway in 1,4-dipolar cycloaddition, utilizing imidazo[5,1- a]isoquinoline and related congeners, would serve as a new route towards the synthesis of spiro[oxindole-3,3'- pyrrolines], a class of diverse biological activities. An insight into the thermodynamic control pathway is presented.

Keywords: N-alkylisatins, cascade reactions, dimethyl acetylenedicarboxylate, kinetic vs. thermodynamic control, 3-phenylimidazo[5, 1- a]isoquinoline, NMR.

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