Network


Latest external collaboration on country level. Dive into details by clicking on the dots.

Hotspot


Dive into the research topics where Diederica D. Claeys is active.

Publication


Featured researches published by Diederica D. Claeys.


Chemistry: A European Journal | 2011

Furan‐Oxidation‐Triggered Inducible DNA Cross‐Linking: Acyclic Versus Cyclic Furan‐Containing Building Blocks—On the Benefit of Restoring the Cyclic Sugar Backbone

Kim B. Stevens; Diederica D. Claeys; Saron Catak; Sara Figaroli; Michal Hocek; Jan M. Tromp; Stefan Schürch; Veronique Van Speybroeck; Annemieke Madder

Oligodeoxynucleotides incorporating a reactive functionality can cause irreversible cross-linking to the target sequence and have been widely studied for their potential in inhibition of gene expression or development of diagnostic probes for gene analysis. Reactive oligonucleotides further show potential in a supramolecular context for the construction of nanometer-sized DNA-based objects. Inspired by the cytochrome P450 catalyzed transformation of furan into a reactive enal species, we recently introduced a furan-oxidation-based methodology for cross-linking of nucleic acids. Previous experiments using a simple acyclic building block equipped with a furan moiety for incorporation into oligodeoxynucleotides have shown that cross-linking occurs in a very fast and efficient way and that substantial amounts of stable, site-selectively cross-linked species can be isolated. Given the destabilization of duplexes observed upon introduction of the initially designed furan-modified building block into DNA duplexes, we explore here the potential benefits of two new building blocks featuring an extended aromatic system and a restored cyclic backbone. Thorough experimental analysis of cross-linking reactions in a series of contexts, combined with theoretical calculations, permit structural characterization of the formed species and allow assessment of the origin of the enhanced cross-link selectivity. Our experiments clearly show that the modular nature of the furan-modified building blocks used in the current cross-linking strategy allow for fine tuning of both yield and selectivity of the interstrand cross-linking reaction.


Organic and Biomolecular Chemistry | 2010

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

Diederica D. Claeys; Christian V. Stevens; Bart Roman; Pieter Van de Caveye; Michel Waroquier; Veronique Van Speybroeck

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 TiCl(4) and FeCl(3) 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 FeCl(3) catalyzed reaction mixture on celite caused complete aromatization.


Journal of Organic Chemistry | 2008

Synthesis of tricyclic phosphonopyrrolidines via IMDAF: Experimental and theoretical investigation of the observed stereoselectivity

Diederica D. Claeys; Kristof Moonen; Bart Roman; Victor N. Nemykin; Viktor V. Zhdankin; Michel Waroquier; Veronique Van Speybroeck; Christian V. Stevens

During the synthesis of tricyclic phosphonopyrrolidines via intramolecular Diels-Alder reactions of 1-acylamino(furan-2-yl)methyl phosphonates, two isomers are formed in most cases. The presence of a short three-atom tether together with spectroscopic data, including difference NOE, revealed that the cycloaddition occurred exo, but the phosphonate substituent on the tether had an exo or endo orientation. This was confirmed via X-ray analysis. A thermodynamic preference for the product with the phosphonate function in the endo position was observed experimentally and was confirmed theoretically. Density functional theory methods and several high-level post Hartree-Fock procedures were used to rationalize the observed isomer ratio of the IMDAF-reactions. This was done for two different types of reagents: with the activating carbonyl group in the tether or as a substituent on the tether. For the first type of molecules there is a large steric hindrance of the bulky tether substituents that disfavors the exo-isomer. In the latter case, there was a very small energy difference between the transition states causing a mixture of epimers being formed.


Journal of Physical Chemistry A | 2010

Conformational Sampling of Macrocyclic Alkenes Using a Kennard―Stone-Based Algorithm

Diederica D. Claeys; Toon Verstraelen; Ewald Pauwels; Christian V. Stevens; Michel Waroquier; Veronique Van Speybroeck

The properties and functions of (bio)molecules are closely related to their molecular conformations. A variety of methods are available to sample the conformational space at a relatively low level of theory. If a higher level of theory is required, the computational cost can be reduced by selecting a uniformly distributed set of conformations from the ensemble of conformations generated at a low level of theory and by optimizing this selected set at a higher level. The generation of conformers is performed using molecular dynamics runs which are analyzed using the MD-Tracks code [J. Chem. Inf. Model. 2008, 48, 2414]. This article presents a Kennard-Stone-based algorithm, with a distance measure based on the distance matrix, for the selection of the most diverse set of conformations. The method has been successfully applied to macrocyclic alkenes. The correct thermodynamic stability of the double-bond isomers of a flexible macrocyclic alkene containing two chiral centers is reproduced. The double-bond configuration has a limited effect on the conformation of the whole macrocycle. The chirality of the stereocenters has a larger effect on the molecular conformations.


European Journal of Organic Chemistry | 2006

The pyroglutamate hydantoin rearrangement

Nicolai Dieltiens; Diederica D. Claeys; Viktor V. Zhdankin; Victor N. Nemykin; Bart Allaert; Francis Verpoort; Christian V. Stevens


RSC Advances | 2013

Accurate prediction of 1H chemical shifts in interstrand cross-linked DNA

Ewald Pauwels; Diederica D. Claeys; José Martins; Michel Waroquier; Giuseppe Bifulco; Veronique Van Speybroeck; Annemieke Madder


Chemical Communications | 2005

Synthesis of 1,3-dioxo-hexahydropyrido[1,2-c][1,3]diazepine carboxylates, a new bicyclic skeleton formed by ring expansion–RCM methodology

Nicolai Dieltiens; Diederica D. Claeys; Bart Allaert; Francis Verpoort; Christian V. Stevens


European Journal of Organic Chemistry | 2008

The Formation of trans‐Fused Macrocycles from N3,N3′‐Polymethylenebis(hydantoins) by Ring‐Closing Metathesis

Diederica D. Claeys; Christian V. Stevens; Nicolai Dieltiens


Journal of Organic Chemistry | 2006

Synthesis of N(3),N‘(3)-Polymethylene-bis-hydantoins and Their Macrocyclic Derivatives

Nicolai Dieltiens; Diederica D. Claeys; Christian V. Stevens


Organic Letters | 2005

Straightforward Ring Expansion of Pyroglutamates to Perhydro-1,3-diazepine-2,4-diones

Christian V. Stevens; Nicolai Dieltiens; Diederica D. Claeys

Collaboration


Dive into the Diederica D. Claeys's collaboration.

Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar
Top Co-Authors

Avatar

Francis Verpoort

Wuhan University of Technology

View shared research outputs
Top Co-Authors

Avatar

Kristof Moonen

Eastman Chemical Company

View shared research outputs
Top Co-Authors

Avatar
Researchain Logo
Decentralizing Knowledge