Molecular mechanism of Diels--Alder reaction between (E)-3,3,3-trichloro-1-nitropropene and cyclopentadiene: B3LYP/6-31G(d) computational study
Analysis of reactivity indexes supports the polar character of the reaction between (E)-3,3,3-trichloro-1-nitropropene and cyclopentadiene. This is confirmed by the analysis of electronic properties of transition complexes involved in the reaction paths using the B3LYP/6-31G(d) algorithm. The transition state's asymmetry is large, but it is insufficient to provoke a zwitterionic reaction mechanism. Attempts to find a heterocyclic intermediate 7 in the reaction path ultimately leading to 5-endo-nitro-6-exo-trichloromethylnorbornene 3 have been unsuccessful.
Molecular mechanism of Diels–Alder reaction between (E)-3,3,3-trichloro-1-nitropropene and cyclopentadiene: B3LYP/6-31G(d) computational study
Analysis of reactivity indexes supports the polar character of the reaction between (E)-3,3,3-trichloro-1-nitropropene and cyclopentadiene. This is confirmed by the analysis of electronic properties of transition complexes involved in the reaction paths using the B3LYP/6-31G(d) algorithm. The transition state's asymmetry is large, but it is insufficient to provoke a zwitterionic reaction mechanism. Attempts to find a heterocyclic intermediate 7 in the reaction path ultimately leading to 5-endo-nitro-6-exo-trichloromethylnorbornene 3 have been unsuccessful.
___
- Jasi´ nski, R.; Kwiatkowska, M.; Sharnin, V.; Bara´ nski, A. Monatsh Chem . 2013, 124, 327–335.
- Novikov, S. S.; Shvekhgeimer, G. A.; Dudinskaya, A. A. Izv Akad. Nauk SSSR (Khimya) 1961, 690–695. Parr, R. G., Szentpaly, L.; Liu, S. J. Am. Chem. Soc. 1999, 121, 1922–1924.
- Bara´ nski, A.; Jasi´ nski, R.; Cholewka, E. In Post¸ epy w in˙zynierii i technologii chemicznej; Kowalski, Z., Ed.; Krakow University of Technology, Krakow, 2011 (in Polish).
- Fringuelli, F.; Taticchi, A. The Diels-Alder Reactions: Selected Practical Methods; J. Wiley & Sons, New York, 200 Jasi´ nski, R.; Kwiatkowska, M.; Bara´ nski, A. Wiad. Chem. 2007, 67, 485–514 (in Polish).
- Korotayev, V. Yu.; Barkov, A. Yu.; Slepukhin, P. A.; Kodess, M. I.; Sosnovskikh, V. Ya. Mendeleev Commun. 2011, 21, 112–114.
- Korotayev, V. Yu.; Sosnovskikh, V. Ya.; Barabanov, M. A.; Barkov, A. Yu.; Kodess, M. I. Mendeleev. Commun. 2010, 20, 17–19.
- Domingo, L. R.; Aurell, M. J.; P´ erez, P.; Contreras, R. Tetrahedron 2002, 58, 4417–4423.
- Jasi´ nski, R.; Bara´ nski, A. J. Mol. Struct. Theochem. 2010, 949, 8–13.
- Steglenko, D. V.; Kletsky, M. E.; Kurbatov, S. V.; Tatarov, A. V.; Minkin, V. I.; Goumont, R.; Terrier, F. J. Phys. Org. Chem. 2009, 20, 298–307.
- P´ erez, P.; Domingo, L. R.; Aizman, A.; Contreras, R. In Theoretical Aspects of Chemical Reactivity ; Toro-Labbe, A., Ed.; Elsevier, Amsterdam, 2007.
- P´ erez, P.; Chamorro, E. Lett. Org. Chem. 2011, 8, 88–94.
- Jasi´ nski, R.; Kwiatkowska, M.; Bara´ nski, A. J. Phys. Org. Chem. 2011, 24, 843–853.
- Kwiatkowska, M.; Jasi´ nski, R.; Mikulska, M.; Bara´ nski, A., Monatsh. Chem. 2010, 141, 545–548.
- Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T. Jr; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, Y.; Honda, O.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, M. C.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I., Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision B.04. Gaussian, Inc., Pittsburgh, 2003.
- Kiselev, V. D.; Konovalov, A. I. J. Phys. Org. Chem. 2009, 22, 466–483.