Serviços Personalizados
Artigo
Indicadores
Links relacionados
-
Citado por Google
-
Similares em Google
Compartilhar
South African Journal of Chemistry
versão On-line ISSN 1996-840X
versão impressa ISSN 0379-4350
S.Afr.j.chem. (Online) vol.64 Durban 2011
RESEARCH ARTICLE
Elucidation of the complex Baylis-Hillman reaction of 3-methoxy-2-nitrobenzaldehyde with methyl vinyl ketone
Kenudl C. Idahosa; Duduzille M. Molefe; Vusumzl E. Pakade; Michael E. Brown ; Perry T. Kaye*
Department of Chemistry and Centre for Chemico- and Biomedicinal Research, Rhodes University, Grahamstown, 6140, South Africa
ABSTRACT
DABCO-catalyzed reaction of 3-methoxy-2-nitrobenzaldehyde with methyl vinyl ketone (MVK) affords a mixture of products, comprising the 'normal' Baylis-Hillman adduct, the MVK dimer and a pair of diastereomeric bis-(MVK)Baylis-Hillman adducts. 1H NMR spectroscopy-based kinetic studies have provided clear insights into the competing pathways and product distribution in this complex reaction.
Keywords: Baylis-Hillman reaction, mechanism, kinetics, 1H NMR spectroscopic analysis, bis-(MVK)Baylis-Hillman products
Full text available only in pdf format.
Acknowledgements
The authors thank the South African Medical Research Council (MRC) for a bursary (D.M.M.), the MRC and Rhodes University for generous financial support and Dr P. Kempgens and A. Soper for assistance with NMR spectroscopy.
References and Notes
1 D. Basavaiah, P.D. Rao and R.S. Hyma, Tetrahedron, 1996, 52(24), 8001-8062. [ Links ]
2 D. Basavaiah, A.J. Rao and T. Satyanarayana, Chem. Rev., 2003,103, 811-892. [ Links ]
3 (a) E. Ciganek, Organic Reactions, 1997, 51, 203-350. [ Links ] (b) S.E. Drewes and G.H.P. Roos, Tetrahedron, 1988, 44(15), 46563-4670. [ Links ]
4 (a) M.L. Bode and P.T. Kaye, Tetrahedron Lett., 1991, 32, 5611-5614. [ Links ] (b) P.T. Kaye, M.A. Musa, X.N. Nocanda and S. Robinson, Org. Biomol. Chem, 2003, 1, 1133-1138. [ Links ]
5 P.T. Kaye and X.W. Nocanda, J. Chem. Soc., Perkin Trans. 1, 2002, 1318-1323. P.T. Kaye, M.A. Musa and X.W. Nocanda, Synthesis, 2003, (4), 531-534. [ Links ]
6 O.B. Familoni, P.J. Klaas, K.A. Lobb, VE. Pakade and P.T. Kaye, Org. Biomol. Chem., 2006, 4, 3960-3965. [ Links ]
7 O.B. Familoni, P.T. Kaye and P.J. Klaas, J. Chem. Soc., Chem. Commun., 1998, 2563-2564. [ Links ]
8 V.E. Pakade, Application of the Bayliss-Hillman Reaction in the Preparation of Quinoline Derivatives, MSc thesis, Rhodes University, 2005. [ Links ]
9 M. Shi, C-Q. Li and J-K. Jiang, Tetrahedron, 2003, 59, 1181-1185. [ Links ]
10 J. Bacsa, P.T. Kaye and R.S. Robinson, S. Afr. J. Chem, 1998, 51,47-54. [ Links ]
11 M. Shi, C-Q. Li and J-K. Jiang, Chem. Commun, 2001, 833-834. [ Links ]
12 M. Shi, C-Q. Li and J-K. Jiang, Molecules, 2002, 7, 721-726. [ Links ]
13 The results of an ongoing theoretical study will be published in due course.
14 Gaussian 03, Revision E.01, 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, V. Bakken, 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, 2004. [ Links ]
15 H. Hu, Q.N. Van, VA. Mandelshtam and A.J. Shaka, J. Magn. Reson., 1998, 134, 76-87. [ Links ]
16 Y. Peng, Q. Ding, Z. Li, G. Wang and J. Cheng, Tetrahedron Lett, 2003, 44, 3871-3875. [ Links ]
Received 17 June 2011
Revised 24 September 2011
Accepted 26 September 2011
Submitted by invitation to celebrate 2011 the 'International Year of Chemistry'.
* To whom correspondence should be addressed. E-mail: p.kaye@ru.ac.za