A Combined Topological ELF, NCI and QTAIM Study of Mechanism and Hydrogen Bond Controlling the Selectivity of the IMDC Reaction of Nitrone-alkene Obtained from m-allyloxybenzaldehyde

Author(s): Fouad Chafaa, Abdelmalek Khorief Nacereddine*, Abdelhafid Djerourou.

Journal Name: Letters in Organic Chemistry

Volume 17 , Issue 4 , 2020

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

The selectivity and molecular mechanism of the intramolecular [3+2] cycloaddition (IMDC) reaction of nitrone-alkene generated from m-allyloxybenzaldehyde has been studied computationally using B3LYP/6-31G(d) theoretical method. The energy profiles indicate that this IMDC reaction favours kinetically the formation of the fused-endo, as observed experimentally. The solvent has no influence on the mechanism and selectivity, but it increases slightly the activation energy and decreases the exothermic character of this IMDC reaction. The analysis through electron localisation function (ELF) of the favourable fused-endo pathway shows that the formation of the C–O and C–C new bonds occurred via a non-concerted synchronous one-step mechanism. The analysis of noncovalent interaction using Non-covalent interaction (NCI) and QTAIM analyses of the structure of the fused-endo transition state indicates that the hydrogen-bond formed at this approach is the origin for the favouring of the fused-endo pathway.

Keywords: Hydrogen-bond, QTAIM, m-allyloxybenzaldehyde, isoxazolidines, DFT calculations, ELF, NCI.

[1]
Carruthers, W. Some Modern Methods of Organic Synthesis, 2nd ed; Cambridge University Press: Cambridge, 1978.
[2]
Padwa, A.; Pearson, W.H. Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products; John Wiley & Sons: Hoboken, NJ, 2003.
[3]
Kobayashi, S.; Jørgensen, K.A. Cycloaddition Reactions in Organic Synthesis; Wiley-VCH: Weinheim, 2002.
[4]
Ding, P.; Miller, M.; Chen, Y.; Helquist, P.; Oliver, A.J.; Wiest, O. Org. Lett., 2004, 6, 1805.
[5]
Koumbis, A.E.; Gallos, J.K. Curr. Org. Chem., 2003, 7, 585.
[6]
Tufariello, J.J. In 1.3-Dipolar Cycloaddition Chemistry; A, Padwa., Ed.; Wiley: New York, 1984, Vol. 2, p. 83.
[7]
(a) Duret, G.; Quinlan, R.; Yin, B.; Martin, R.E.; Bisseret, P.; Neuburger, M.; Blanchard, N. J. Org. Chem., 2017, 82, 1726.
(b) Chafaa, F.; Hellel, D.; Nacereddine, A.K.; Djerourou, A. Tetrahedron Lett., 2016, 57, 67.
(c) Domingo, L.R.; Ríos-Gutiérrez, M.; Adjieufack, A.I.; Ndassa, I.M.; Nouhou, C.N.; Mbadcam, J.K. ChemistrySelect, 2018, 3, 5412.
[8]
Hazra, A.; Bharitkar, Y.P.; Maity, A.; Mondal, S.; Mondal, N.B. Tetrahedron Lett., 2013, 54, 4339.
[9]
Eyring, H. J. Chem. Phys., 1935, 3, 107.
[10]
Becke, A.D.; Edgecombe, K.E. J. Chem. Phys., 1990, 92, 5397.
[11]
(a) Johnson, E.R.; Keinan, S.; Mori-Sanchez, P.; Contreras-Garcia, J.; Cohen, J.; Yang, A.W. J. Am. Chem. Soc., 2010, 132, 6498.
(b) Lane, J.R.; Contreras-Garcia, J.; Piquemal, J.P.; Miller, B.J.; Kjaergaard, H.G. J. Chem. Theory Comput., 2013, 9, 3263.
(c) Contreras-Garcia, J.E.; Johnson, R.; Keinan, S.; Chaudret, R.; Piquemal, J.P.; Beratan, D.N.; Yang, W. J. Chem. Theory Comput., 2011, 7, 625.
[12]
Frisch, M.J.; 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.; Peralta, J.E., Jr; 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, J.M.; 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.; Salvador, P.; Dannenberg, J.J.; Dapprich, S.; Daniels, A.D.; Farkas, O.; Foresman, J.B.; Ortiz, J.V.; Cioslowski, J.; Fox, D. Gaussian 09, Revision A.02; Gaussian: Wallingford, CT, 2009.
[13]
(a) Lee, C.; Yang, W.; Parr, R.G. Phys. Rev. B Condens. Matter Mater. Phys., 1988, 37, 785.
(b) Becke, A.D. J. Chem. Phys., 1993, 98, 5648.
(c) Hehre, W.J.; Radom, L.; Schleyer, P.V.R.; Pople, J.A. ab initio Molecular Orbital Theory; Wiley: New York. , 1986.
[14]
(a) Tomasi, J.; Persico, M. Chem. Rev., 1994, 94, 2027.
(b) Simkin, B.Y.; Sheikhet, I. Quantum Chemical and Statistical Theory of Solutions A Computational Approach; Ellis Horwood: London, 1995.
[15]
(a) Cances, E.; Mennucci, B.; Tomasi, J. J. Chem. Phys., 1997, 107, 3032.
(b) Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett., 1996, 255, 327.
(c) Barone, V.; Cossi, M.; Tomasi, J. J. Comput. Chem., 1998, 19, 404.
[16]
Becke, A.D. J. Chem. Phys., 1993, 98, 5648.
[17]
(a) Reed, A.E.; Weinstock, R.B.; Weinhold, F. J. Chem. Phys., 1985, 83, 735.
(b) Reed, A.E.; Curtiss, L.A.; Weinhold, F. Chem. Rev., 1988, 88, 899.
[18]
Lu, T.; Chen, F. J. Comput. Chem., 2012, 33, 580.
[19]
(a) Nacereddine, A.K.; Yahia, W.; Bouacha, S.; Djerourou, A. Tetrahedron Lett., 2010, 51, 2617.
(b) Nacereddine, A.K.; Sobhi, C.; Djerourou, A.; Ríos-Gutiérrez, M.; Domingo, L.R. RSC Advances, 2015, 5, 99299.
(c) Chafaa, F.; Hellel, D.; Nacereddine, A.K.; Djerourou, A. Mol. Phys., 2016, 114, 663.
(d) Hellel, D.; Chafaa, F.; Nacereddine, A.K.; Djerourou, A.; Vrancken, E. RSC Advances, 2017, 7, 30128.
[20]
(a) Nacereddine, A.K.; Layeb, H.; Chafaa, F.; Yahia, W.; Djerourou, A.; Domingo, L.R. RSC Advances, 2015, 5, 64098.
(b) Nasri, L.; Ríos-Gutiérrez, M.; Nacereddine, A.K.; Djerourou, A.; Domingo, L.R. Theor. Chem. Acc., 2017, 136, 104.
[21]
Bader, R.F.W. Atoms in Molecules. A Quantum Theory; Claredon Press: Oxford, U.K, 1990.
[22]
(a) Rozas, I.; Alkorta, I.; Elguero, J. J. Am. Chem. Soc., 2000, 122, 11154.
(b) Grabowski, S.J.; Sokalski, W.A.; Dyguda, E.; Leszczynski, J. J. Phys. Chem. B, 2006, 110, 6444.
[23]
Rozas, I.; Alkorta, I.; Elguero, J. J. Am. Chem. Soc., 2000, 122, 11154.


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 17
ISSUE: 4
Year: 2020
Page: [260 - 267]
Pages: 8
DOI: 10.2174/1570178616666190401202143
Price: $65

Article Metrics

PDF: 14
HTML: 3