A theoretical investigation on the mechanism of cycloaddition reactions of fulvenes with tetrazine and diazacyclopentadienone derivatives
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The mechanism of cycloaddition reactions for 6-dimethylaminofulvene and 6,6-diphenylfulvene with tetrazine and diazacyclopentadienone are studied by DFT at the MPWB1K/cc-pVDZ level of theory. The energy results indicated that the [6 + 4] cycloaddition reaction of 6-dimethylaminofulvene with tetrazine and diazacyclopentadienone derivatives proceeds in a stepwise fashion, while the [2 + 4] cycloaddition reaction of 6,6-diphenylfulvene might proceed in a one-step fashion. Our calculations showed some unfavorable processes with unstable cycloadducts arising from [4 + 2] cycloaddition reactions which are unobserved in the experimental results. Also, an analysis of the Parr functions for the reactants allows us to provide an explanation of the selectivity of these cycloaddition reactions.
KeywordsCycloaddition reactions One-step Stepwise Fulvene Density functional theory Domino reaction
The authors wish to acknowledge Dr. Louise S. Price, University College London, UK, for reading the manuscript and providing valuable suggestions.
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- 1.Neuenschwander M (1989) The chemistry of double-bonded functional groups. In S Patai (Ed.), Wiley, ChichesterGoogle Scholar
- 3.Noyori R, Hayakawa Y, Takaya H, Murai S, Kobayashi R, Sonoda N (1978) Carbon-carbon bond formation promoted by transition metal carbonyls. 16. Reaction of α,α-dibromo ketones and iron carbonyls. Mechanistic aspects. J Am Chem Soc 100:1759–1765. https://doi.org/10.1021/ja00474a018 CrossRefGoogle Scholar
- 4.Imafuku K, Arai K (1989) A simple and convenient synthesis of 5-alkyl-substituted 3-isopropenyl-and 3-acetyltropolones synthesis, 501–505Google Scholar
- 7.Himeda Y, Yamataka H, Ueda I, Hatanaka M (1997) [3 + 2] annulation of allylidenetriphenylphosphorane with 1,2-diacylethylenes and 1,2-diacylacetylenes: a concerted synthesis of tri- and tetrasubstituted cyclopentadienes and fulvenes. J Org Chem 62:6529–6653. https://doi.org/10.1021/jo970594x8 CrossRefGoogle Scholar
- 8.Nair V, Nair AG Radhakrishnan VM, Nadakumar V, Rath NP (1997) Diels-Alder reactions of a 6-arenyl fulvene participating both as diene and dienophile. Synlett:767–768. https://doi.org/10.1055/s-1997-5763
- 15.Öcal N, Bağdatli E, Arslan M (2005) Diels-Alder reactions of new methoxysubstituted-6-arylfulvenes. Turk J Chem 29:7–16Google Scholar
- 24.Paddon-Row MN, Watson PL, Warrener RN (1973) Application of PMO theory to the problem of perispecificity in cross-conjugated systems with special attention to the isobenzofulvene nucleus. Tetrahedron Lett:1033–1036. https://doi.org/10.1016/S0040-4039(01)95897-6
- 29.Rhyman L, Ramasami P, Joule JA, Sáeza JA, Domingo LR (2013) Understanding the formation of [3 + 2] and [2 + 4] cycloadducts in the Lewis acid catalysed reaction between methyl glyoxylate oxime and cyclopentadiene: a theoretical study. RSC Adv 3:447–457. https://doi.org/10.1039/C2RA22332E CrossRefGoogle Scholar
- 32.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JAJ, Start-mann RE, Burant JC, Daprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochtersk JI, Petersson GA, Ayala Y, Ui QC, Morokuma K, Malick DK, Rubuck AD, Raghavachari K, Foresman JB, Cioslowski J, Oritz JV, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Comperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challa-combe M, Gill MW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (2009) Gaussian 09 revision A.02. Gaussian, Inc, WallingfordGoogle Scholar
- 33.Hehre WJ, Radom L, PVR S, Pople JA (1986) Ab initio molecular orbital theory. Wiley, New YorkGoogle Scholar
- 39.Parr RG, Yang W (1989) Density functional theory of atoms, molecules. Oxford University Press, New YorkGoogle Scholar
- 44.Parr RG, Yang W (1995) Density-functional theory of the electronic structure of molecules. Annu Rev Phys Chem 46:701–728. https://doi.org/10.1146/annurev.pc.46.100195.003413 CrossRefPubMedGoogle Scholar
- 45.Chermette H (1999) Chemical reactivity indexes in density functional theory. J Comput Chem 20:129–154. https://doi.org/10.1002/(SICI)1096-987X(19990115)20:1 CrossRefGoogle Scholar