A DFT investigation of the Diels–Alder reaction of ethyl propiolate to the cage-annulated hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione
Main Article Content
Abstract
The Diels–Alder (DA) reaction between the cage-annulated diene hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione (HHDD) with a cyclohexa-1,3-diene moiety and ethyl propiolate (EP) dienophile was investigated by the DFT method at the B3LYP/6-31+G(d,p) level to elucidate the mechanism and regioselectivity features of the reaction. The geometrical and electronic structures of the caged diene HHDD and EP were studied at B3LYP/6-31+G(d,p) level. In order to identify facial- and regio-selectivity of the DA reaction of HHDD and EP, the frontier molecular orbital (FMO) interactions of the reactants according to the FMO theory, and the molecular electrostatic potential map of HHDD were examined. The potential energy surface (PES) of the related DA reaction was calculated, and optimizations of transition states and of products corresponding to critical points on the PES were performed at the B3LYP/6-31+G(d,p), and their configurations were determined. In addition, the thermodynamic and kinetic parameters of each possible cycloaddition reaction were calculated using the B3LYP/6-31+G(d,p) method to determine whether the reaction occurs under thermodynamic or kinetic control. The thermochemical results showed that the related DA cycloaddition proceeds under kinetic control, and the activation energies of syn cycloadditions are clearly lower than that of anti cycloadditions. The theoretical calculations are in good agreement with experimental results.
Downloads
Metrics
Article Details
Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution license 4.0 that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
References
T. C. Chou, P. C. Hong, Y. F. Wu, W. Y. Chang, C. T. Lin, Tetrahedron 52 (1996) 6325
G. Mehta, R. Uma, Tetrahedron Letters 36 (1995) 4873
J. M. Coxon, S. T. Fong, D. Q. McDonald, P. J. Steel, Tetrahedron Lett. 34 (1993) 163
W. D. Fessner, C. Grund, H. Prinzbach, Tetrahedron Lett. 32 (1991) 5935
J. M. Coxon, R. G. A. R. Maclagan, D. Q. McDonald, P. J. Steel, J. Org. Chem. 56 (1991) 2542
J. M. Coxon, S. T. Fong, K. Lundie, D. Q. McDonald, P. J. Steel, A. P. Marchand, F. Zaragoza, U. R. Zope, D. Rajagopal, S. G. Bott, W. H. Watson, R. P. Kashyap, Tetrahedron 50 (1994) 13037
A. S. Kushner, Tetrahedron Letters 12 (1971) 3275
B. Pandey, U. R. Zope, N. R. Ayyangar, J. Chem. Soc.,Chem. Commun. 2 (1990) 107
a) A. P. Marchand, H. S. Chong, B. Ganguly, R. Shukla, E. Z. Dong, A. Hazlewood, T. D. Power, W. H. Watson, S. G. Bott, Tetrahedron 57 (2001) 8629 b) A. P. Marchand, H.-S. Chong, B. Ganguly, J. M. Coxon, Croatica Chemica Acta 73 (2000) 1027
L. Salem, J. Am. Chem. Soc. 90 (1968) 543
L. Salem, J. Am. Chem. Soc. 90 (1968) 553
K. Fukui, Acc. Chem. Res. 4 (1971) 57
K. N. Houk, Acc. Chem. Res. 8 (1975) 361
K. N. Houk, in Pericyclic Reactions, A.P. Marchand, R.E. Lehr, (Eds.) Academic Press, New York, 1977
K. Fukui, Angew. Chem., Int. Ed. 21 (1982) 801
D. G. Truhlar, A. J. Kuppermann, J. Am. Chem. Soc. 93 (1971) 1840
R. Bonaccorsi, E. Scrocco, J. Tomasi, J. Chem. Phys. 52 (1970) 5270
A. D. Becke, J. Chem. Phys. 98 (1993) 5648
C. Lee, W. Yang, R. G. Parr, Phys. Rev., B 37 (1988) 785
R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 72 (1980) 650
C. Gonzalez, H. B. Schlegel, J. Chem. Phys. 90 (1989) 2154
C. Gonzalez, H. B. Schlegel, J. Phys. Chem. 94 (2002) 5523
M. T. Cances, V. Mennucci, J. Tomasi, J. Chem. Phys. 107 (1997) 3032
S. Miertus, E. Scrocco, J. Tomasi, Chem. Phys. 55 (1981) 117
V. Barone, M. Cossi, J. Tomassi, J. Chem. Phys. 107 (1997) 3210
Gaussian 03, Revision B.03, Gaussian Inc., Pittsburgh PA, 2003
G. Klopman, J. Am. Chem. Soc. 90 (1968) 223
L. Fleming, Frontier Orbitals and Organic Chemical Reactions, John Wiley & Sons, London, 1977
T. Lipinska, Tetrahedron 61 (2005) 8148
A. E. Hayden, J. de Chancie, A. H. George, M. Dai, M. Yu, S. J. Danishefsky, K. N. Houk, J. Org. Chem. 74 (2009) 6770
J. S. Murray, D. Yepes, P. Jaque, P. Politzer, Comput. Theor. Chem. 1053 (2015) 270.