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South African Journal of Chemistry

On-line version ISSN 1996-840X
Print version ISSN 0379-4350

S.Afr.j.chem. (Online) vol.62  Durban  2009

 

RESEARCH ARTICLE

 

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

 

 

Parvesh SinghI; Krishna BisettyI; Mohinder P. MahajanII

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

 

 


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


 

 

Full text available only in PDF format.

 

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.

 

References

1 (a) W. Carruthers, in Cycloaddition Reactions in Organic Synthesis; Tetrahedron Organic Chemistry Series, Vol. 8, Pergamon Press, Elmsford, NY, USA, 1990;         [ Links ] (b) F. Pontén and G. Magnusson, J. Org. Chem., 1997, 62, 7978-7983; (c) B.-C. Hing, S.-S. Sun and Y.-C. Tsai, J. Org. Chem., 1997, 62, 7717-7725.         [ Links ]

2 (a) O. Diels and K. Alder, Justus Liebigs Ann. Chem., 1928, 460, 98-122;         [ Links ] (b) J.A. Norton, Chem. Rev., 1942, 31, 319-523;         [ Links ] (c) L.W. Butz and A.W Rytina, Org. React., 1949, 5, 136-192;         [ Links ] (d) J. Sauer, Angew. Chem., Int. Ed. Engl., 1966, 5, 211-230;         [ Links ] (e) H. Kault and K. King, Chem. Rev., 1968, 68, 415-447;         [ Links ] (f) J.G. Martin and R.K. Hill, Chem. Rev., 1961, 61, 537-562;         [ Links ] (g) L.C. Dias, J. Braz. Chem. Soc., 1997, 8, 289-332;         [ Links ] (h) K.N. Houk, J. González and Y. Li, Acc. Chem. Res., 1995, 28, 81-90;         [ Links ] (i) K.N. Houk, Y. Li and J.D. Evanseck, Angew. Chem., Int. Ed. Engl., 1992, 31, 682-688;         [ Links ] (j) B.A. Horn, J.L. Herek and A.H. Zewail, J. Am. Chem. Soc., 1996, 118, 8755-8756.         [ Links ]

3 (a) W. Oppolzer, Angew. Chem, Int. Ed. Engl., 1977, 16, 10-24;         [ Links ] (b) J. Sauer and R. Sustmann, Angew. Chem., Int. Ed. Engl., 1980, 19, 779-807.         [ Links ]

4 (a) A.K. Sharma, S. Jayakumar, M.S. Hundal and M.P. Mahajan, J. Chem. Soc. Perkin Trans. 1, 2002, 774-784;         [ Links ] (b) P.D. Dey, A.K. Sharma, P.V. Bharatam and M.P. Mahajan, Tetrahedron, 1997, 53, 13829-13840;         [ Links ] (c) S. Jayakumar, M.P.S. Ishar and M.P. Mahajan, Tetrahedron, 2002, 58, 379-471;         [ Links ] (d) S. Jayakumar, P. Singh and M.P. Mahajan, Tetrahedron, 2004, 60, 4315-4324;         [ Links ] (e) C. Mohan, P. Singh and M.P. Mahajan, Tetrahedron, 2005, 61, 10774-10780;         [ Links ] (f) P. Singh, A. Marwaha, H. Singh and M.P. Mahajan, Tetrahedron, 2005, 61, 11999-12005.         [ Links ]

5 (a) S. Motoki, Y. Matsuo, Y. Terauchi, Bull. Chem. Soc. Jpn., 1990, 63, 284-286;         [ Links ] (b) T. Saito, H. Kimura, K. Sakamaki, T. Karakasa and S. Moriyama, Chem. Commun., 1996, 811-812;         [ Links ] (c) O. Tsuge, T. Hatta, H. Yoshitomi, K. Kurosaka, T. Fujiwara, H. Maeda and A. Kakehi, Heterocycles, 1999, 50, 661-663;         [ Links ] (d) C. Spino, G. Liu, N. Tu and S. Girard, J. Org. Chem., 1994, 59, 5596-5608;         [ Links ] (e) C. Spino and G. Liu, J. Org. Chem., 1993, 58, 817-825;         [ Links ] (e) O. Tsuge, T. Hatta, K. Yakata and H. Maeda, Chem. Lett., 1994, 1833-1836;         [ Links ] (f) O. Tsuge, T. Hatta, H. Yoshitomi, K. Kurusaka and A. Kakehi, presented at the 65th National Meeting of the Chemical Society of Japan, Tokyo, 1993, Abstr. II, 3A513, 98;         [ Links ] O. Tsuge, T. Hatta, H. Yoshitomi, T. Fujiwara, presented at the 67th National Meeting of the Chemical Society of Japan, Tokyo, 1994, Abstr. II, 2J130, 1027.         [ Links ]

6 T. Saito, H. Kimura, T. Chonan, T. Soda and T. Karakasa, Chem. Commun., 1997, 11, 1013-1014.         [ Links ]

7 (a) W.E. Truce, D.J. Abraham and P. Son, J. Org. Chem., 1966, 32, 990-997;         [ Links ] (b) K. Bogdanowicz-Szwed and A. Palasz, Monatsh. Chem., 1995, 126, 1341-1348.         [ Links ]

8 A. Bargagna, P. Schenone, F. Bondavalli and M. Longobardi, J. Heterocycl. Chem., 1982, 19, 257-261.         [ Links ]

9 Accelrys, Materials Studio Release Notes, Release 4.1, Accelrys Software, Inc., San Diego, CA, USA, 2006.         [ Links ]

10 Gaussian 03, Revision A.1, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, VG. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. V Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez and J.A. Pople, Gaussian, Inc., Wallingford, CT, USA, 2003.         [ Links ]

11 (a) A.D. Becke, J. Chem. Phys., 1993, 98, 5648-5652;         [ Links ] (b) C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785-789.         [ Links ]

12 R. Cammi and J. Tomasi, J. Comput. Chem, 1995, 16, 1449-1458.         [ Links ]

13 (a) M.H. Elnagdi, S.M. Mousawi, M.M. Abdel-Khalik, S. El-Sheriny and E. John, J. Heterocycl. Chem., 2001, 38, 949-953.         [ Links ]

14 S.K. Chatterjee and W.-D. Rudorf, Phosphorus, Sulfur Silicon Relat. Elem, 1998, 133, 251-266.         [ Links ]

15 R.F. Abdullah and R.S. Brinkmeyer, Tetrahedron, 1979, 35, 1675-1735.         [ Links ]

 

 

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

 

 

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

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