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Participation of Phosphorylated Analogues of Nitroethene in Diels–Alder Reactions with Anthracene: A Molecular Electron Density Theory Study and Mechanistic Aspect

Agnieszka Kącka-Zych

Organics · pp. 36–48 · Published 23 Nov 2020

10.3390/org1010004

Abstract

The structure and the contribution of the bis(2-chloroethyl) 2-nitro 1a and 2-bromo-2-nitroethenylphosphonates 1b with anthracene 2 in the Diels–Alder (DA) reactions have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP functional together with 6-31G(d), 6-31+G(d) and 6-31+G(d,p) basic sets. Analysis of the Conceptual Density Functional Theory (CDFT) reactivity indices indicates that 1a and 1b can be classified as a strong electrophile and marginal nucleophile, while 2 is classified as a strong electrophile and strong nucleophile. The studied DA reactions take place through a one-step mechanism. A Bonding Evolution Theory (BET) of the one path associated with the DA reaction of 1a with 2 indicates that it is associated with non-concerted two-stage one-step mechanism. BET analysis shows that the first C2-C3 single bond is formed in Phase VI, while the second C1-C6 single bond is formed in the Phase VIII. The formation of both single bonds occurs through the merging of two C2 and C3, C1 and C6 pseudoradical centers, respectively.

Nucleophile Electrophile Chemistry Density functional theory Anthracene Nitro Reactivity (psychology) Computational chemistry

References (42)

  1. 1 Coarey, 2002, Catalytic enantioselective Diels--Alder reactions: Methods, mechanistic fundamentals, pathways, and applications [DOI]
  2. 2 Nicolaou, 2002, The Diels–Alder Reaction in Total Synthesis [DOI]
  3. 3 Heravi, 2015, Recent applications of the hetero Diels–Alder reaction in the total synthesis of natural products [DOI]
  4. 4 Feuer, H. (2008). Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis: Novel Strategies in Synthesis, John Wiley & Sons. [2nd ed.]. [DOI]
  5. 5 2020, Molecular mechanism of Hetero Diels-Alder reactions between (E)-1,1,1-trifluoro-3-nitrobut-2-enes and enamine systems in the light of Molecular Electron Density Theory [DOI]
  6. 6 Korotaev, 2011, Diastereoselective reactions of 1,1,1-trichloro(trifluoro)-3-nitrobut-2-enes with 2-morpholinoalk-1-enes [DOI]
  7. 7 Korotaev, 2011, Uncatalyzed reactions of α-(trihaloethylidene)nitroalkanes with push–pull enamines: A new type of ring–ring tautomerism in cyclobutane derivatives and the dramatic effect of the trihalomethyl group on the reaction pathway [DOI]
  8. 8 Lee, 1978, Diels-Alder Reaction of Pyrrole with Dimethyl Acetylenedicarboxylate [DOI]
  9. 9 Domingo, 1998, Toward an Understanding of the Molecular Mechanism of the Reaction between 1-Methylpyrrole and Dimethyl Acetylenedicarboxylate. An ab Initio Study [DOI]
  10. 10 Anisimova, 2005, Reactions of 2-Nitro- and 2-Bromo-2-nitroethenylphosphonates with Anthracene [DOI]
  11. 11 Domingo, L.R. (2016). Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry. Molecules, 21. [DOI]
  12. 12 Krokidis, 1997, Characterization of elementary chemical processes by catastrophe theory [DOI]
  13. 13 Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Vreven, T.J., Kudin, K.N., and Burant, J.C. (2016). Gaussian 16 Rev A.1, Gaussian Inc.
  14. 14 Stephens, 1994, Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields [DOI]
  15. 15 Dresler, 2018, Regioselectivity, stereoselectivity, and molecular mechanism of [3 + 2] cycloaddition reactions between 2-methyl-1-nitroprop-1-ene and (Z)-C-aryl-N-phenylnitrones: A DFT computational study [DOI]
  16. 16 Kącka-Zych, A. (2019). Understanding the molecular mechanism of the rearrangement of internal nitronic ester into nitronorbornene in light of the MEDT study. Molecules, 24. [DOI]
  17. 17 2019, Unexpected molecular mechanism of trimethylsilyl bromide elimination from 2-(trimethylsilyloxy)-3-bromo-3-methyl-isoxazolidines [DOI]
  18. 18 Domingo, 2019, A molecular electron density theory study of the Lewis acid–catalyzed decomposition reaction of nitroethyl benzoate using aluminum derivatives [DOI]
  19. 19 Domingo, L.R., Ríos-Gutiérrez, M., and Pérez, P. (2020). Unveiling the Lewis Acid Catalyzed Diels–Alder Reactions through the Molecular Electron Density Theory. Molecules, 25. [DOI]
  20. 20 Fukui, 1970, Formulation of the reaction coordinate [DOI]
  21. 21 Tapia, 1992, Solvent effect theories: Quantum and classical formalism and their applications in chemistry and biochemistry [DOI]
  22. 22 Tomasi, 1994, Molecular interactions in solution: An overview of methods based on continuous distributions of the solvent [DOI]
  23. 23 Simkin, Y., and Sheikhet, I. (1995). Quantum Chemical and Statistical Theory of Solutions: A Computational Approach, Ellis Horwood.
  24. 24 Cances, 1997, A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics [DOI]
  25. 25 Cossi, 1996, Ab initio study of solvated molecules: A new implementation of the polarizable continuum model
  26. 26 Domingo, 2014, A new C–C bond formation model based on the quantum chemical topology of electron density [DOI]
  27. 27 Reed, 1985, Natural population analysis [DOI]
  28. 28 Reed, 1988, Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint [DOI]
  29. 29 Greelings, 2003, Conceptual density functional theory [DOI]
  30. 30 Domingo, L.R., Ríos-Gutiérrez, M., and Pérez, P. (2016). Applications of the conceptual density functional theory indices to organic chemistry reactivity. Molecules, 21. [DOI]
  31. 31 Parr, 1999, Electrophilicity index [DOI]
  32. 32 Domingo, 2008, Understanding the Reactivity of Captodative Ethylenes in Polar Cycloaddition Reactions. A Theoretical Study [DOI]
  33. 33 Domingo, 2013, Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions [DOI]
  34. 34 Becke, 1990, A simple measure of electron localization in atomic and molecular systems [DOI]
  35. 35 Noury, 1999, Computational tools for the electron localization function topological analysis [DOI]
  36. 36 Dennington, R., Keith, T.A., and Millam, J.M. (2016). GaussView Version 6.1, Semichem Inc.
  37. 37 Ahrens, J., Geveci, B., and Law, C. (2005). ParaView: An End-User Tool for Large Data Visualization. Visualization Handbook, Elsevier. [DOI]
  38. 38 Ayachit, U. (2015). The ParaView Guide: A Parallel Visualization Application, Kitware.
  39. 39 2020, Push-pull nitronates in the [3+2] cycloaddition with nitroethylene: Molecular Electron Density Theory study [DOI]
  40. 40 Parr, R.G., and Yang, W. (1989). Density Functional Theory of Atoms and Molecules, Oxford University Press.
  41. 41 Domingo, 2002, Quantitative characterization of the global electrophilicity power of common diene/dienophile pairs in Diels–Alder reactions [DOI]
  42. 42 Jaramillo, 2008, A further exploration of a nucleophilicity index based on the gas-phase ionization potentials [DOI]

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