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Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields

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Abstract
Diphosphonylated diazaheterocyclic compounds were synthesized in a one-step reaction by using dimethyl trimethylsilyl phosphite (DMPTMS) under acidic conditions. The reaction of DMPTMS with 1,5-naphthyridine yielded the corresponding diphosphonylated product through a tandem 1,4-1,2 addition under microwave conditions. This tandem 1,4-1,2 addition was also evaluated for other substrates, namely, 1,10-phenanthroline, 1,7-phenanthroline and 4,7-phenanthroline. Reactions under reflux and microwave conditions were compared. 1,5-Naphthyridine and the phenanthroline derived substrates are less reactive than previously investi-gated quinolines. The experimental trends in reactivity were rationalized by means of theoretical calculations. The intrinsic properties, such as aromaticity and proton affinities, showed distinct differences for the various substrates. Furthermore, the calculated free energies of activation for the rate-determining step of the tandem addition reaction enabled us to rationalize the differences in product yields. Both the theoretical and the experimental results show the substantial influence of the position of the nitrogen atoms in the (poly) aromatic compounds on the reaction outcome.
Keywords
MECHANISM, CHEMISTRY, ESTERS, PHOSPHONIC ACIDS, Nitrogen heterocycles, Nucleophilic addition, Phosphonylation, Density functional calculations, INDEPENDENT CHEMICAL-SHIFTS, TRIMETHYL PHOSPHITE, CRYSTAL-STRUCTURE, BETA-UNSATURATED IMINES, ALPHA, STACKING, CATIONS

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MLA
De Blieck, Ann, Saron Catak, Wouter Debrouwer, et al. “Diphosphonylation of Aromatic Diazaheterocycles and Theoretical Rationalization of Product Yields.” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2013.6 (2013): 1058–1067. Print.
APA
De Blieck, Ann, Catak, S., Debrouwer, W., Drabowicz, J., Hemelsoet, K., Verstraelen, T., Waroquier, M., et al. (2013). Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2013(6), 1058–1067.
Chicago author-date
De Blieck, Ann, Saron Catak, Wouter Debrouwer, Józef Drabowicz, Karen Hemelsoet, Toon Verstraelen, Michel Waroquier, Veronique Van Speybroeck, and Christian Stevens. 2013. “Diphosphonylation of Aromatic Diazaheterocycles and Theoretical Rationalization of Product Yields.” European Journal of Organic Chemistry 2013 (6): 1058–1067.
Chicago author-date (all authors)
De Blieck, Ann, Saron Catak, Wouter Debrouwer, Józef Drabowicz, Karen Hemelsoet, Toon Verstraelen, Michel Waroquier, Veronique Van Speybroeck, and Christian Stevens. 2013. “Diphosphonylation of Aromatic Diazaheterocycles and Theoretical Rationalization of Product Yields.” European Journal of Organic Chemistry 2013 (6): 1058–1067.
Vancouver
1.
De Blieck A, Catak S, Debrouwer W, Drabowicz J, Hemelsoet K, Verstraelen T, et al. Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. 2013;2013(6):1058–67.
IEEE
[1]
A. De Blieck et al., “Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields,” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, vol. 2013, no. 6, pp. 1058–1067, 2013.
@article{3191221,
  abstract     = {Diphosphonylated diazaheterocyclic compounds were synthesized in a one-step reaction by using dimethyl trimethylsilyl phosphite (DMPTMS) under acidic conditions. The reaction of DMPTMS with 1,5-naphthyridine yielded the corresponding diphosphonylated product through a tandem 1,4-1,2 addition under microwave conditions. This tandem 1,4-1,2 addition was also evaluated for other substrates, namely, 1,10-phenanthroline, 1,7-phenanthroline and 4,7-phenanthroline. Reactions under reflux and microwave conditions were compared. 1,5-Naphthyridine and the phenanthroline derived substrates are less reactive than previously investi-gated quinolines. The experimental trends in reactivity were rationalized by means of theoretical calculations. The intrinsic properties, such as aromaticity and proton affinities, showed distinct differences for the various substrates. Furthermore, the calculated free energies of activation for the rate-determining step of the tandem addition reaction enabled us to rationalize the differences in product yields. Both the theoretical and the experimental results show the substantial influence of the position of the nitrogen atoms in the (poly) aromatic compounds on the reaction outcome.},
  author       = {De Blieck, Ann and Catak, Saron and Debrouwer, Wouter and Drabowicz, Józef and Hemelsoet, Karen and Verstraelen, Toon and Waroquier, Michel and Van Speybroeck, Veronique and Stevens, Christian},
  issn         = {1434-193X},
  journal      = {EUROPEAN JOURNAL OF ORGANIC CHEMISTRY},
  keywords     = {MECHANISM,CHEMISTRY,ESTERS,PHOSPHONIC ACIDS,Nitrogen heterocycles,Nucleophilic addition,Phosphonylation,Density functional calculations,INDEPENDENT CHEMICAL-SHIFTS,TRIMETHYL PHOSPHITE,CRYSTAL-STRUCTURE,BETA-UNSATURATED IMINES,ALPHA,STACKING,CATIONS},
  language     = {eng},
  number       = {6},
  pages        = {1058--1067},
  title        = {Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields},
  url          = {http://dx.doi.org/10.1002/ejoc.201201437},
  volume       = {2013},
  year         = {2013},
}

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