An unprecedented "reverse" 1,2-migration of a nitro group within an α-aryl-β-nitroethenyl moiety driven by steric and stereoelectronic effects

Letters in Organic Chemistry

Volumn 4, Issue 4, 2007, Pages 268-272

  Bianchi, Lara ^a   Giorgi, Gianluca ^b   Maccagno, Massimo ^a   Petrillo, Giovanni ^a   Rizzato, Egon ^c   Spinelli, Domenico ^c   Stenta, Marco ^c   Tavani, Cinzia ^a  

^a UNIVERSITY OF GENOA   (Italy)

^b UNIVERSITY OF SIENA   (Italy)

^c UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

DFT calculations; Isoxazoline N oxides; Nitro group migration; Nitroalkenes; Vinylcyclopropanes

Indexed keywords

EID: 35649003076     PISSN: 15701786     EISSN: None     Source Type: Journal    
DOI: 10.2174/157017807781024165     Document Type: Article

References (25)

1. (a) Dell'Erba, C.; Spinelli, D.; Leandri, G. J. Chem. Soc. Chem. Commun., 1969, 549;
2. (b) Dell'Erba, C.; Mele, A.; Novi, M.; Petrillo, G.; Stagnaro, P. Tetrahedron Lett., 1990, 31, 4933.
3. (a) Bianchi, L.; Dell'Erba, C.; Maccagno, M.; Morganti, S.; Petrillo, G.; Rizzato, E.; Sancassan, F.; Severi, E.; Spinelli, D.; Tavani, C. Arkivoc, 2000 (vii), 169;
4. (b) Armaroli, T.; Dell'Erba, C.; Gabellini, A.; Gasparrini, F.; Mugnoli, A.; Novi, M.; Petrillo, G.; Tavani, C. Eur. J. Org. Chem., 2002, 1284;
5. (c) Bianchi, L; Dell'Erba, C.; Gasparrini, F.; Novi, M.; Petrillo, G.; Sancassan, E; Tavani, C. Arkivoc, 2002, 142;
6. (d) Dell'Erba, C.; Gabellini, A.; Mugnoli, A.; Novi, M.; Petrillo, G.; Tavani, C. Tetrahedron, 2001, 57, 9025, and previous papers in the series.
7. As far as the role of NaI is concerned, a mechanism for its catalytic effect within the nitrocyclopropane to isoxazoline N-oxide isomerization has been already advanced [2c]. A discussion on its possible role in the nitro-group migration will be provided in the forthcoming full paper.
8. 2 for all reflections for non-H atoms by using the SHELXL-97 [4c] program. Crystallographic data (excluding structure factors) for the structures in the paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers CCDC 608814 (A (7a)) and CCDC 608815 (B (8a)). Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: 144-(0)1223-336033 or e-mail: depositγcdc.cam.ac.uk).
9. (b) Sheldrick, G. M., SHELXS-97, Rel. 97-2, A program for automatic solution of crystal structures, Göttingen University, 1997.
10. (c) Sheldrick, G. M., SHELXL-97, Rel. 97-2, A program for crystal structure refinement, Göttingen University, 1997.
11. (a) Leseticky, L.; Fidler, V.; Prochazka, M. Collec. Czech. Chem. Commun., 1973, 38, 459;
12. (b) Leseticky, L.; Prochazka, M. Collec. Czech. Chem. Commun., 1971, 36, 307;
13. (c) Kral, V.; Leseticky, L. Collec. Czech. Chem. Commun., 1975, 40, 2816;
14. (d) Hesse, G.; Jager, V. Liebigs Ann. Chem., 1970, 740, 85.
15. (a) Guerrera, F.; Salerno, L.; Lamartina, L.; Spinelli, D. J. Chem. Soc. Perkin Trans. 1, 1995, 1243;
16. (b) Spinelli, D.; Zanirato, P.; di Miceli, E.; Lamartina, L.; Guerrera, F. J. Org. Chem., 1997, 62, 4921;
17. (c) Cosimelli, B.; Lamartina, L.; Spinelli, D. Tetrahedron, 2001, 57, 8903;
18. (d) Cosimelli, B.; Lamartina, L.; Lanza, C. Z.; Spinelli, D.; Spisani, R.; Vegna, F. Tetrahedron, 2003, 59, 7189.
19. Williams, D. L. H. In Supplement F2: The Chemistry of Amino, Nitroso, Nitro and Related Groups; Patai, S., Ed.; Wiley: New York, 1996.
20. DFT calculations have been carried out using the Gaussian-03 series of programs [9]. The structures of the various minima points have been fully optimized with the gradient method. After the gas-phase optimization, single point calculations in solution were performed. The correctness of such a methodology was checked by means of a full-optimization calculation considering the solvent. In each case the solvent (ε 46.7) was treated with the SCRF-CPCM method [10]. The calculations were performed using the DFT level and the B3LYP functional, available in Gaussian-03. All atoms were assigned the double-Z DZVP [11] basis-set.
21. Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; 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, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; 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, O.; 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. and Pople, J. A. Gaussian, Inc., Wallingford CT, 2004.
22. (a) Cammi, R.; Mennucci, B.; Tomasi, J. J. Phys. Chem. A, 2000, 104, 5631;
23. (b) Barone, V.; Cossi, M. J. Phys. Chem. A, 1998, 102, 1995.
24. DZVP basis set is a Local Spin Density (LSD)-optimized basis set of double-Z quality in the valence shell plus polarization functions, (a) Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Can. J. Chem., 1992, 70, 560;
25. (b) UniChem DGauss, Version 2.31, 1994, Cray Research, Inc.