Regio- and stereoselectivity of the 1,3-dipolar cycloaddition of azomethine ylides to (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-ones: A combined experimental and theoretical study

Essam M. Hussein, Ziad Moussa, Uttam Pal, Reem I. Alsantali, Abdullah Y.A. Alzahrani, Rami J. Obaid, Fawaz M. Alzahrani, Munirah M. Al-Rooqi, Meshari A. Alsharif, Nizar El Guesmi, Rabab S. Jassas, M. Shaheer Malik, Hatem M. Altass, Samir K. Pal, Tanusri Saha Dasgupta, Saleh A. Ahmed

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

Functionalized oxindoles and pyrrolizidines form the central structural framework for numerous natural products with extensive biological and pharmacological applications. The requirement for high regio- and stereoselectivity is the main obstacle in the synthesis of such five-membered heterocycles. Multicomponent cycloaddition reactions often provide an efficient and straightforward approach for the preparation of specific regio- and stereoisomers. In this article, the regio- and stereochemistry of the polar [3 + 2]-cycloaddition (32CA) reaction of azomethine ylides prepared by the reaction of isatin derivatives and L-proline with a series of (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-ones was investigated by experimental and theoretical methods. Among the isatin and (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one derivatives, a remarkable inversion of regioselectivity was observed in the 32CA reaction of azomethine ylide generated by the reaction of L-proline and 5-chloroisatin or N-methyl-5-chloroisatin with (E)-5-chloro-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one. The regio- and stereochemical assignment of the structures of the cycloaddition products was determined by one- and two-dimensional (1D&2D) homonuclear and heteronuclear correlation nuclear magnetic resonance spectroscopy. The molecular mechanism as well as the regio- and stereoselectivity of the cycloaddition were investigated by means of global and local reactivity indices and a density functional theory (DFT) and explained in detail on the basis of the transition state stabilities of the reactants.

Original languageEnglish
Article number103855
JournalArabian Journal of Chemistry
Volume15
Issue number6
DOIs
Publication statusPublished - Jun 2022

Keywords

  • DFT
  • Local reactivity
  • Multicomponent [3 + 2] cycloaddition
  • Natural product scaffold
  • Transition state

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering

Fingerprint

Dive into the research topics of 'Regio- and stereoselectivity of the 1,3-dipolar cycloaddition of azomethine ylides to (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-ones: A combined experimental and theoretical study'. Together they form a unique fingerprint.

Cite this