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

wim — Tue, 13 Sep 2011 11:48:06 +0000

D.D. Claeys, C.V. Stevens, B.I. Roman, P. Van De Caveye, M. Waroquier, V. Van Speybroeck

Organic & Biomolecular Chemistry

8, 3644-3654

2010

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 α-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.

DOI

http://dx.doi.org/10.1039/C002926B

Private attachment

10 org. & biomolecular chem 8, 3644 claeys.pdf

Cleavage of the Oxanorbornene Oxygen Bridge with Lewis Acids: Computation and Experiment

wim — Tue, 18 Oct 2011 07:01:00 +0000

D.D. Claeys, K. Moonen, B.I. Roman, P. Van De Caveye, V. Van Speybroeck, M. Waroquier, C.V. Stevens

Poster

Conference / event / venue

13th ICQC congres

Helsinki, Finland

Monday, 22 June, 2009 to Saturday, 27 June, 2009

Abstract

2009 abstract_ICQC09_claeys_d.pdf

Center for Molecular Modeling - P. Van De Caveye

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

Abstract

DOI

Private attachment

Cleavage of the Oxanorbornene Oxygen Bridge with Lewis Acids: Computation and Experiment

Conference / event / venue

Abstract