Abstract
The B3LYP/6-31G(d) simulations of competing CDA and HDA reactions between cyclopentadiene and (E)-2-arylnitroethenes prove that regardless of the medium polarity, the processes leading to respective 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3,4 (paths A and B) should be most favoured, and the more electrophilic (E)-2-(p-nitrophenyl)-nitroethene should be more reactive than the less electrophilic (E)-2-(p-methoxyphenyl)-nitroethene. Asymmetry of the transition complexes on the favoured pathways increases with increase of medium polarity, but not sufficiently to enforce the zwitterionic mechanism. Analysis of competing pathways leading to HDA adducts proves that not all these compounds can be formed directly from the adducts. In particular, on the path C, the initially formed 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3 is converted to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nona-3,7-diene N-oxides 5 as a result of a [3.3]-sigmatropic shift. On the paths D–F leading to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nonadienes N-oxides 6–8, the reaction proceeds according to a one-step mechanism.
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R. Jasiński, O.I. Koifman, A. Barański, Mendeleev Commun. (2011) (In press)
R. Jasiński, M. Kwiatkowska, A. Barański, J. Phys. Org. Chem. (2011) (In press) DOI: 10.1002/poc.1853
R. Jasiński, P. Michorczyk, E. Jasińska, O. Koifman, A. Barański, Izv. Vuzov. Khimya i Khim. Tekhnol. 54, 89 (2011) (In Russian)
R. Jasiński, A. Barański, J. Mol. Struct. (TheoChem) 949, 8 (2010)
R. Jasiński, M. Rzyman, A. Barański., Coll. Czech. Chem. Commun. 75, 919 (2010)
M. Kwiatkowska, R. Jasiński, M. Mikulska, A. Barański, Monatsh. Chem. 141, 545 (2010)
R. Jasiński, M. Kwiatkowska, A. Barański, J. Mol. Struct. (TheoChem) 910, 80 (2009).
M.I. Mangione, A.M. Sarotti, A.G. Suárez, R.A. Spanevello, Carbohydrate Research 346, 460 (2011)
R.S. Paton, J.L. Mackey, W.H. Kim, J.H. Lee, S.J. Danishefsky, K.N. Houk, J. Am. Chem. Soc. 132, 9335 (2010)
M.V. Gomez, A.I. Aranda, A. Moreno, F.P. Cossıo, A. Cozar, A. Dıaz-Ortiz, A. Hoz, P. Prieto, Tetrahedron 65, 5328 (2009)
N. Çelebi-Ölçüm, D.H. Ess, V. Aviyente, K.N. Houk, J. Org. Chem. 73, 7472 (2008).
N. Ono, The nitro group in organic synthesis (Wiley-VCH, Weinheim, 2001)
S.E. Denmark, A. Thorarensen, Chem. Rev. 96, 137 (1996)
P. Perez, L.R. Domingo, A. Aizman, R. Contreras, In: A. Toro-Labbé (Ed.), Theoretical and Computational Chemistry (Elsevier, Amsterdam, 2007) vol. 19
M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, T. Jr. 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, Y. Nakajima, O. 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, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, M.C., 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,. J.A. Pople, Gaussian 03, Revision B.04 (Gaussian, Inc., Pittsburgh PA, 2003)
M. Barone, M. Cossi, J. Tomasi, J. Comp. Chem. 19, 404 (1998)
R.K. Nesbet, Variational principles and methods in theoretical physics and chemistry (Cambridge University Press, Cambridge, 2003)
M. Bujak, A. Barański, Czasopismo Tech. PK. (Chemia), 1 (2002) (In Polish); Chem. Abstr. 140, 270441
V.D. Kiselev, A.I. Konovalov, Russ. Chem. Bull., Int. Ed. 52, 293 (2003)
V.D. Kiselev, A.I. Konovalov, J. Phys. Org. Chem. 22, 466 (2009)
G. Leroy, M. Sana, L.A. Burke, M.T. Nguyen, Quantum Theory Chem. React. 1, 91 (1980)
L.R. Domingo, M.J. Aurell, P. Perez, R. Contreras, J. Org. Chem. 68, 3884 (2003)
R. Jasiński, M. Kwiatkowska, A. Barański, Wiad. Chem. 61, 485 (2007)
R.B. Woodward, R. Hoffmann, The Conservation of Orbital Symmetry (Verlag Chemie Academic Press, Weinheim & New York, 2004)
E.V. Anslyn, D.A. Dougherty, Modern physical organic chemistry (University Science Books, California, 2006)
P.A. Wade, J.K. Murray Jr., S. Shah-Patel, P.J. Carroll, Tetrahedron Lett. 43, 2585 (2002)
P.A. Wade, J.K. Murray Jr., S. Shah-Patel, H.T. Lee, Chem. Commun. 1090 (2002)
D.V. Steglenko, M.E. Kletsky, S.V. Kurbatov, A.V. Tatarov, V. I. Minkin, R. Goumont, F. Terrier, J. Phys. Org. Chem. 20, 298 (2009)
A. Pipic, PhD thesis (Drexel University, 2010)
L.R. Domingo, M.J. Aurell, M.N. Kneeteman, P.M. Mancini, J. Mol. Struct. (TheoChem) 853, 68 (2008)
P. Arroyo, M.T. Picher, L.R. Domingo, J. Mol. Struct. (TheoChem) 709, 45(2004)
L.R. Domingo, A. Asensio, P. Arroyo, J. Phys. Org. Chem. 15 660, (2002)
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Part 8 of the series ‘Conjugated Nitroalkenes in Cycloaddition Reactions’; Part 7 see Ref. [1].
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Jasiński, R., Koifman, O. & Barański, A. A B3LYP/6-31G(d) study of Diels-Alder reactions between cyclopentadiene and (E)-2-arylnitroethenes. cent.eur.j.chem. 9, 1008–1018 (2011). https://doi.org/10.2478/s11532-011-0088-5
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DOI: https://doi.org/10.2478/s11532-011-0088-5