A theoretical study on the regio- and stereoselectivity of [3+2] cycloddition of β-trifluoroacetyl vinyl ethyl ether with 3-oxo-1,2-pyrazolidinium ylides

Mina haghdadi, Nasim Nab


[3+2] cycloaddition reactions of β-trifluoroacetyl vinyl ethyl ether (1) with substituted and unsubstitued 3-oxo-1,2-pyrazolidinium ylides (2a-2e) were studied by using density functional theory (DFT) methods at the cc-pVDZ level. The mechanistic details of these reactions, especially with respect to regio- and stereoselectivity, were analyzed. Analysis of the relative energies which were associated with the different reaction pathways indicates the presence of the trifluoroacetyl group in the dipolarophile and substituents on the aryl ring in the dipolar have a remarkable effect on selectivity. Also, it is found that the ortho-endo pathway with the lowest activation energy is preferred, which is in good agreement with the experimental data. Moreover, the elimination of ethanol from [3+2] cycloadducts and the formation of bicyclic pyrazolidinones are explained in order to give a total description of the complete domino processes. The inclusion of solvent effects increases the activation energies and the exothermic character of cycloadducts, but does not change the gas phase selectivity. DFT-based reactivity indices clearly predict the experimental regiochemistry.


DFT study; trifluoroacetyl group; 3-oxopyrazolidin-2-ium-1-ide; reactivity indices; cycloaddition reaction; bicyclic pyrazolidinone

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A. Padwa, in 1,3dipolar Cycloaddition Chemistry. Vol. 1, Ed., Wiley, New York, 1984, p. 732

V. K. Gothelf, K. A. Jørgensen, In Asymmetric Reactions in Synthetic Applications of 1,3dipolar Cycloaddition Chemistry toward Heterocycles and Natural Products, A. Padwa, W. H. Pearson, Wiley & Sons, Hoboken, NJ, 2003

R. Grashey, In Azomethine Imines in 1,3dipolar Cycloaddition Chemistry, A. Padwa, Wiley, New York, 1984

B. Stanovnik, Tetrahedron 47 (1991) 2925

M. Ẑličar, B. Stanovnik, M. Tišler, Tetrahedron 48 (1992) 7965

M. Ẑličar, B. Stanovnik, M. Tišler, J. Heterocycl. Chem. 30 (1993) 1209

T. Oishi, K. Yamagushi, N. Mizuno, Chem. Lett. 39 (2010) 1057

B. Stanovnik, B. Jelen, C. Turk, M. Ẑličar, J. Svete, J. Heterocycl. Chem. 35 (1998) 1187

H. Dorn, Chem. Heterocycl. Compd. USSR 3 (1981), and references cited therein.

R. M. Claramunt, J. Elguero,. Org. Proc. Prep. Int. 23 (1991) 273

R. J. Ternansky, S. E. Draheim, Tetrahedron 48 (1992) 777

J. Svete, A. Prešeren, B. Stanovnik, L. Golič, S. Golič Grdadolnik, J. Heterocycl. Chem. 34 (1997) 1323

W. O, Gotfresden, S. Vargedal, Acta Chem. Scand. 9 (1955) 1498

H. Dorn, A. Otto, Chem. Ber. 101 (1968) 3287

F. Roussi, A. Chauveau, M. Bonin, L. Micouin, H. P. Husson, Synthesis 41 (2000) 1179

A. Chauveau, T. Martens, M. Bonin, L. Micouin, H. P. Husson, Synthesis 13 (2002) 1890

R. J. Ternansky, S. E. Draheim, Tetrahedron Lett. 31 (1990) 2808

R. E. Holmes, D. A. Neel, Tetrahedron Lett. 31 (1990) 5570

H. Dorn, Tetrahedron Lett. 26 (1985) 5126

K. Yoshimura, K. Yamaguchi, N. Mizuno, Chem. Lett. 39 (2010) 1087

W. Chen, X. H. Yuan, R. Li, W. Du, Y. Wu, L. S. Ding, Y. C. Chen, Adv. Synth. Catal. 348 (2006) 1822

M. P. Sibi, D. Rane, L. M. Stanley, T. Soeta. Org. Lett. 10 (2008) 2974

K. Tanaka, T. Kato, Y. Ukaji, K. Inomata, Heterocycles 80 (2010) 893

R. Shintani, T. Hayashi, J. Am. Chem. Soc. 128 (2006) 6331; N. D. Shapiro, Y. Shi, F. D. Toste, J. Am. Chem. Soc. 131 (2009) 11655; S. Chassaing, A. Alix, T. Boningari, K. Sani Souna Sido, M. Keller, P. Kuhn, B. Louis, J. Sommer, P. Pale, Synthesis 9 (2010) 1567

Y. Xin, J. W. Zhao, J. Gu, S. Z. Zhu, J. Fluorine Chem. 132 (2011) 402

J. M. Indelicato, C. E. Pasini, J. Med. Chem. 31 (1988) 1230

; D. J. Steenkamp, D. Weldrick, H. S. C. Spies, Eur. J. Biochem. 242 (1996) 566

K. Tanaka, T. Mori, K. Mitsuhashi, Bull. Chem. Soc. Jpn. 66 (1993) 263

S. Bigotti, L. Malpezzi, M. Molteni, A. Mele, W. Panzeri, M. Zanda, Tetrahedron Lett. 50 (2009) 2540

J. Jekowiecki, R. Loska, M. Meekelleche, Tetrahedron 63 (2007) 4464

P. Lin, J. Jiang, Tetrahedron 56 (2000) 3635

T. K. Das, S. Salampuria, M. Banerjee, Comput. Theor. Chem. 979 (2012) 102

R. G. Parr, L. V. Szentpaly, S. Liu, J. Am. Chem. Soc. 121 (1999) 1922

M. Ríos-Gutiérrez, A. K. Nacereddine, F. Chafaa, A. Djerourou, L. R. Domingo, J. Mol. Graph. Model. 70 (2016) 304

A. D. Becke, Phys. Rev .A. 38 (1988) 3098; C. Lee, W. Yang, R. G. Parr, Phys. Rev., B 37 (1988) 785

L. Simon, J. M. Goodman, Org. Biomol. Chem. 9 (2011) 689

L. R. Domingo, M. J. Aurell, P. Pérez, Tetrahedron 70 (2014) 4519

Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford, CT

W. J. Hehre, L. Radom, P.v.R. Schleyer, J. A. Pople, Ab initio molecular orbital theory, Vol. 7, Wiley, New York, 1986, p. 379

J. Tomasi, M. Persico, Chem. Rew. 94 (1994) 2027; B. Y. Simkin, I. Sheikhet, Quantum chemical and statistical theory of solutions-A computational approach, Ellis Horod, London, 1995

E. Cances, B. Mennucci, J. Tomasi, J. Chem. Phys. 107 (1997) 3032; M. Cossi, V. Barone, R. Cammi, J. Tomasi, Chem. Phys. Lett. 255 (1996) 327

L. R. Domingo, RSC Adv. 4 (2014) 32415; L. R. Domingo, M. Rios-Gutiérrez, P. Pérez, Tetrahedron 72 (2016) 1532

A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem. Phys. 83 (1985) 735

R. G. Parr, W. Yang, Density functional theory of atoms and molecules, Oxford, 1989; R. G. Parr, R. C. Pearson, J. Am. Chem. Soc. 105 (1983) 7512

R. G. Parr, L. V. Szentplay, S. Liu, J. Am. Chem. Soc. 121 (1999) 1922

L. R. Domingo, P. Pérez, J. Org. Chem. 73 (2008) 4615; L. R. Domingo, P. Pérez, Org. Biomol. Chem. 9 (2011) 7168

W. Kohn, L. Sham, J. Phys. Rev., A 140 (1965) 1133

L. R. Domingo, P. Pérez, J. A. Saez, RSC Adv. 3 (2013) 1486

C. Gonzalez, H. B. Schlegel, J. Phys. Chem. 94 (1990) 5523

K. B. Wiberg, Tetrahedron 24(1968) 1083

L. R. Domingo, J. A. Saez, Org. Biomol. Chem. 7 (2009) 3576

R. G. Parr, W. Yang, Ann. Rev. Phys. Chem. 46(1995) 701; H. Chermette, J. Comput. Chem. 20(1999) 129

D. H. Ess, G. O. Jones, K. N. Houk, Adv. Synth. Catal. 348 (2006) 2337

P. Jaramillo, L. R. Domingo, E. Chamorro, P. Pérez, J. Mol. Struct. THEOCHEM 865 (2008) 68

L. R. Domingo, M. J. Aurell, P. Pérez, R. Contreras, Tetrahedron 58 (2002) 4417

L. R. Domingo, S. R. Emanian, Tetrahedron 70 (2014) 1267

H. Chemouri, S. M. Mekellecche, Int, J. Quantum Chem. 112 (2012) 2294.

DOI: http://dx.doi.org/10.2298/JSC170511099H


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