M. Barbero et al. / Tetrahedron 69 (2013) 3212e3217
3217
2. Barbero, M.; Cadamuro, S.; Ghigo, G.; Dughera, S. Org. Biomol. Chem. 2012, 10,
4058 and references cited therein.
3. Hendrickson, J. B.; Okano, S.; Bloom, R. K. J. Org. Chem. 1969, 34, 3434.
4. King, J. F.; Guo, Z. R. Unpublished results cited in: King, J. F. In The Chemistry of
Sulphonic Acids, Esters and Their Derivatives; Patai, S., Ed.; John Wiley: New York,
NY, 1991; Chapter 6, pp 249e259.
The
DpKa between the picric acid and the studied compounds
correspond to the chemical equilibrium reported in paragraph of
Section 2.1.
4.6. Computational method
€
~
5. Zerbe, E.-M.; Wolper, C.; Roca Pinol, S.; Jones, P. G.; Blaschette, A. Z. Anorg. Allg.
Chem. 2007, 633, 593.
6. (a) Ho, J.; Coote, M. L. Theor. Chem. Acc. 2010, 125, 3; (b) Kelly, C. P.; Cramer, C. J.;
Truhlar, D. G. J. Phys. Chem. A 2006, 110, 2493; (c) Bryantsev, V. S.; Diallo, M. S.;
Goddard, W. A., III. J. Phys. Chem. B 2008, 112, 9709; (d) Trummal, A.; Rummel,
A.; Lippmaa, E.; Burk, P.; Koppel, I. A. J. Phys. Chem. A 2009, 113, 6206.
7. Kutt, A.; Rodima, T.; Saame, J.; Raamat, E.; Maemets, V.; Kaljurand, I.; Koppel, I.
A.; Garlyauskayte, R. Y.; Yagupolskii, Y. L.; Yagupolskii, L. M.; Bernhardt, E.;
Willner, H.; Leito, I. J. Org. Chem. 2011, 76, 391 and references cited therein.
8. Norberg, K. Acta Chem. Scand. 1966, 20, 264.
All structures (acids and conjugated anion bases) were optimized
using the density functional method (DFT),23 with the recently de-
veloped functional M06-2X24 with the 6-31þG(d,p)25aec basis set,
and using vibrational analysis to check the nature of the critical
points26 (all data are reported in Supplementary data). The energy
values were then refined using single-point calculations with the
basis set 6-311þG(3df,2p),25d and combined with the thermal cor-
rections obtained with the smaller basis set to give free energy values.
Solvent effects were introduced both in geometry optimization and
single-point calculations using the polarized continuum method
(IEF-PCM)27 within the universal solvation model density (SMD).28
Calculations were performed by the quantum package Gaussian 09-
A.02.29 Fig. 2 was obtained using the graphical program Molden.30
€
€
9. Barbero, M.; Bazzi, S.; Cadamuro, S.; Di Bari, L.; Dughera, S.; Ghigo, G.; Padula,
D.; Tabasso, S. Tetrahedron 2011, 67, 5789.
10. Kislyi, K. A.; Samet, A. B.; Semenov, V. V. Russ. J. Org. Chem. 2006, 42, 292.
11. (a) Barbero, M.; Cadamuro, S.; Dughera, S.; Venturello, P. Synlett 2007, 2209; (b)
Barbero, M.; Cadamuro, S.; Dughera, S.; Venturello, P. Synthesis 2008, 1379.
12. Barbero, M.; Cadamuro, S.; Dughera, S.; Venturello, P. Synthesis 2008, 3625.
13. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S. Eur. J. Org. Chem. 2009, 430.
14. Barbero, M.; Cadamuro, S.; Deagostino, A.; Dughera, S.; Larini, P.; Occhiato, E.
G.; Prandi, C.; Tabasso, S.; Vulcano, R.; Venturello, P. Synthesis 2009, 2260.
15. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S.; Ghigo, G. Eur. J. Org. Chem.
2009, 4346.
16. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S.; Piccinini, P. Synthesis 2010,
315.
17. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S. Tetrahedron Lett. 2010, 51, 2342.
18. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S. Tetrahedron Lett. 2010, 51, 6356.
19. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S.; Magistris, C.; Smarra, A.;
Venturello, P. Org. Biomol. Chem. 2011, 9, 2192.
20. Barbero, M.; Cadamuro, S.; Dughera, S.; Magistris, C.; Venturello, P. Org. Biomol.
Chem. 2011, 9, 8393.
21. Fritz, J. S.; Lisicki, N. M. Anal. Chem. 1951, 23, 589.
22. Norberg, K. Talanta 1966, 13, 745.
23. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford
University Press: New York, NY, 1989; Chapter 3.
24. (a) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215; (b) Zhao, Y.; Truhlar,
D. G. Acc. Chem. Res. 2008, 41, 157.
25. (a) McLean, A. D.; Chandler, G. S. J. Chem. Phys. 1980, 72, 5639; (b) Clark, T.;
Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4,
294; (c) Raghavachari, K.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys.
1980, 72, 650; (d) Frisch, M. J.; Pople, J. A.; Binkley, J. S. J. Chem. Phys. 1984, 80,
3265.
26. Reaction free energies were computed as outlined, for instance, in: (a)
Foresman, J. B.; Frisch, Æ. Exploring Chemistry with Electronic Structure Methods;
Gaussian: Pittsburgh, PA, USA, 1996; pp 166e168; (b) McQuarrie, D. A. Statis-
tical Thermodynamics; Harper and Row: New York, NY, 1973.
27. (a) Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, 1995; (b) Cossi, M.; Rega, N.;
Fig. 2. HOMO in 3,5-dinitrobenzenedisulfonimide anion.
Acknowledgements
ꢀ
Scalmani, G.; Barone, V. J. Chem. Phys. 2001, 114, 5691; (c) Cances, M. T.;
Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032; (d) Cossi, M.; Barone, V.;
Mennucci, B.; Tomasi, J. Chem. Phys. Lett. 1998, 286, 253; (e) Mennucci, B.;
Tomasi, J. J. Chem. Phys. 1997, 106, 5151.
This work was supported by the University of Torino.
28. (a) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378;
(b) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 4538.
29. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.;
Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.;
Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers,
E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N.
J.; Klene, M.; Knox, J. E.; 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.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.;
Supplementary data
Total (in au) and relative (in kcal molꢀ1) electronic energies and
free energy corrections are reported. Nuclear coordinates (in A)
follows. Supplementary data associated with this article can be
most important compounds described in this article.
ꢁ
References and notes
€
Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman,
J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.02; Gaussian:
Wallingford, CT, 2009.
1. Barbero, M.; Bazzi, S.; Cadamuro, S.; Dughera, S. Curr. Org. Chem. 2011, 15, 576
and references cited therein.
30. Molden: Schaftenaar, G.; Noordik, J. H. J. Comput.-Aided Mol. Des. 2000, 14, 123.