RESEARCH ARTICLE

 

Computational and experimental studies on the hetero-Diels-Alder reactions of cross-conjugated enaminones with sulphene

 

 

Parvesh Singh^I; Krishna Bisetty^I; Mohinder P. Mahajan^II

^IDepartment of Chemistry, Durban University of Technology, Steve Biko Campus, P. O. Box 1334, Durban 4000, South Africa
^IIDepartment of Applied Chemistry, Guru Nanak Dev University, Amritsar 143005, Punjab, India

 

 

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ABSTRACT

Ab initio and density functional theory (DFT) calculations have been used to investigate the feasibility of cycloaddition reactions of enaminones 1 with sulphene. Specifically, the geometry optimizations, frequency calculations and self-consistent reaction-field (SCRF) solvent simulations in combination with higher-quality relative energies carried out at the DFT level using the 6-31 + G(d) basis set suggests that the product obtained is both thermodynamically and kinetically preferred, indicating the feasibility of this reaction. Additionally, experimental studies carried out on the reactions of these enaminones 1 with sulphene were also found to be in agreement with the theoretical predictions resulting in the synthesis of a variety of novel oxathiine derivatives having great biological and medicinal importance.

Keywords: Enaminones, cycloadditions, sulphene, DFT, SCRF

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Acknowledgements

The authors are grateful to CSIR, New Delhi, for financial support under Grant No. 01(1872/03/EMR-II) and to the Department of Chemistry, GNDU, Amritsar, and RSIC (CDRI), Lucknow, for assistance with spectral data. Financial assistance from the National Research Foundation (NRF) and the Centre for Research Management and Development (CRMD), DUT, for a postdoctoral fellowship is gratefully acknowledged.

 

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Received 25 September 2008
Revised 6 November 2008
Accepted 15 December 2008

 

 

* To whom correspondence should be addressed. E-mail: bisettyk@dut.ac.za