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Experimental and computational study of the ring opening of tricyclic oxanorbornenes to polyhydro isoindole phosphonates

(2010) ORGANIC & BIOMOLECULAR CHEMISTRY. 8(16). p.3644-3654
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
Phosphonylated azaheterocycles are an important class of compounds with high biological potential as conformationally restricted bioisosteres of amino acids. Therefore, it is of interest to synthesize conformationally constrained amino phosphonates. We wanted to investigate possible routes via ring opening of alpha-amino phosphonates with an oxanorbornene skeleton, as these can be synthesized with high stereoselectivity. This was achieved using different Lewis acids, leading to a range of products. The reaction with TiCl4 and FeCl3 was modelled at a DFT level of theory to get insight in the pathways towards the corresponding products. To ease the work up, the Fe(III) catalyst was coated on montmorillonite clay, but this accelerated aromatization after ring opening. Quenching the FeCl3 catalyzed reaction mixture on celite caused complete aromatization.
Keywords
IMDAF CYCLOADDITION, DENSITY-FUNCTIONAL THEORY, MONTMORILLONITE K10, AMINOPHOSPHONIC ACIDS, BIOLOGICAL-ACTIVITY, MOLECULAR CALCULATIONS, AB-INITIO, DIELS-ALDER REACTIONS, OXABICYCLIC ALKENES, EFFECTIVE CORE POTENTIALS

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Citation

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Chicago
Claeys, Diederica, Christian Stevens, Bart Roman, Pieter Van de Caveye, Michel Waroquier, and Veronique Van Speybroeck. 2010. “Experimental and Computational Study of the Ring Opening of Tricyclic Oxanorbornenes to Polyhydro Isoindole Phosphonates.” Organic & Biomolecular Chemistry 8 (16): 3644–3654.
APA
Claeys, Diederica, Stevens, C., Roman, B., Van de Caveye, P., Waroquier, M., & Van Speybroeck, V. (2010). Experimental and computational study of the ring opening of tricyclic oxanorbornenes to polyhydro isoindole phosphonates. ORGANIC & BIOMOLECULAR CHEMISTRY, 8(16), 3644–3654.
Vancouver
1.
Claeys D, Stevens C, Roman B, Van de Caveye P, Waroquier M, Van Speybroeck V. Experimental and computational study of the ring opening of tricyclic oxanorbornenes to polyhydro isoindole phosphonates. ORGANIC & BIOMOLECULAR CHEMISTRY. 2010;8(16):3644–54.
MLA
Claeys, Diederica, Christian Stevens, Bart Roman, et al. “Experimental and Computational Study of the Ring Opening of Tricyclic Oxanorbornenes to Polyhydro Isoindole Phosphonates.” ORGANIC & BIOMOLECULAR CHEMISTRY 8.16 (2010): 3644–3654. Print.
@article{1027212,
  abstract     = {Phosphonylated azaheterocycles are an important class of compounds with high biological potential as conformationally restricted bioisosteres of amino acids. Therefore, it is of interest to synthesize conformationally constrained amino phosphonates. We wanted to investigate possible routes via ring opening of alpha-amino phosphonates with an oxanorbornene skeleton, as these can be synthesized with high stereoselectivity. This was achieved using different Lewis acids, leading to a range of products. The reaction with TiCl4 and FeCl3 was modelled at a DFT level of theory to get insight in the pathways towards the corresponding products. To ease the work up, the Fe(III) catalyst was coated on montmorillonite clay, but this accelerated aromatization after ring opening. Quenching the FeCl3 catalyzed reaction mixture on celite caused complete aromatization.},
  author       = {Claeys, Diederica and Stevens, Christian and Roman, Bart and Van de Caveye, Pieter and Waroquier, Michel and Van Speybroeck, Veronique},
  issn         = {1477-0520},
  journal      = {ORGANIC \& BIOMOLECULAR CHEMISTRY},
  keyword      = {IMDAF CYCLOADDITION,DENSITY-FUNCTIONAL THEORY,MONTMORILLONITE K10,AMINOPHOSPHONIC ACIDS,BIOLOGICAL-ACTIVITY,MOLECULAR CALCULATIONS,AB-INITIO,DIELS-ALDER REACTIONS,OXABICYCLIC ALKENES,EFFECTIVE CORE POTENTIALS},
  language     = {eng},
  number       = {16},
  pages        = {3644--3654},
  title        = {Experimental and computational study of the ring opening of tricyclic oxanorbornenes to polyhydro isoindole phosphonates},
  url          = {http://dx.doi.org/10.1039/c002926b},
  volume       = {8},
  year         = {2010},
}

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