105-09-9Relevant articles and documents
A Modular Synthesis of Multidentate S-, N- and O-Containing Meta- and Paracyclophanes
Rasheed, Omer K.,Bailey, Patrick D.,Lawrence, Amy,Quayle, Peter,Raftery, James
, p. 6988 - 6993 (2015)
The development of a modular approach to macrocycle assembly has enabled the synthesis of a library of pyridine-based macrocycles possessing multiple donor sites where chirality was readily introduced from (R)- or (S)-alanine, a representative amino acid. The facile, regioselective, nucleophilic ring opening of aziridines by dithiols enabled the synthesis of thioether-based linkers which on subsequent alkylation provided access to optically pure macrocycles. A modular approach to macrocyclic assembly has enabled the synthesis of a library of macrocycles possessing multiple donor sites where chirality was readily introduced from (S)-alanine. Key to this approach was the facile, regioselective, nucleophilic ring opening of aziridines by dithiols followed by macrocylisation under conditions of high dilution.
Stereoretentive Ring-Opening Metathesis Polymerization to Access All- cis Poly(p-phenylenevinylene)s with Living Characteristics
Hsu, Ting-Wei,Kim, Cheoljae,Michaudel, Quentin
, p. 11983 - 11987 (2020)
Poly(p-phenylenevinylene)s (PPVs), a staple of the conductive polymer family, consist of alternating alkene and phenyl groups in conjugation. The physical properties of this organic material are intimately linked to the cis/trans configuration of the alkene groups. While many synthetic methods afford PPVs with all-trans stereochemistry, very few deliver the all-cis congeners. We report herein a synthesis of all-cis PPVs with living characteristics via stereoretentive ring-opening metathesis polymerization (ROMP). Exquisite catalyst control allows for the preparation of homopolymers or diblock copolymers with perfect stereoselectivity, narrow dispersities, and predictable average molar masses. All-cis PPVs can then serve as light-responsive polymers through clean photoisomerization of the stilbenoid units.
Synthesis and photophysics of new pyridyl end-capped 3D-dithia[3.3]paracyclophane-based Janus tectons: Surface-confined self-assembly of their model pedestal on HOPG
Attias, A.-J.,Auffray, M.,Charra, F.,Kreher, D.,Mathevet, F.,Sosa Vargas, L.
, p. 7665 - 7674 (2020)
Surface-confined supramolecular self-assembly is currently a promising strategy to create well-organised 2D-networks on conducting surfaces. However, using such substrates tends to quench any electronic properties of the adsorbed molecules. In this context, new pyridyl end-capped 3D-dithia[3.3]paracyclophane-based molecules were designed, along with their model compound (pedestal), with the objective of self-assembling these tectons on any substrate. The synthesis of these new molecules was not straightforward and is consequently described in detail. Once the materials were successfully isolated, their optoelectronic properties were investigated to study potential non-covalent interactions: through pH-dependent absorption and emission measurements, and infra-red spectrometry. We evidenced that both ionic bonding and coordination bonding are compatible with the molecules design. Finally, preliminary scanning tunneling microscopy (STM) studies were performed to study the supramolecular self-assembly properties of the model lower-deck (pedestal) on highly oriented pyrolytic graphite (HOPG): we observed a quasi-square lattice of self-assembled 2D-networks that appear to form independently of the underlying HOPG lattice.
Alkyl substituted [2.2]paracyclophane-1,9-dienes
Lidster, Benjamin J.,Kumar, Dharam R.,Spring, Andrew M.,Yu, Chin-Yang,Helliwell, Madeleine,Raftery, James,Turner, Michael L.
, p. 6079 - 6087 (2016)
[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.
Water-soluble trithiolato-bridged dinuclear ruthenium(II) and osmium(II) arene complexes with bisphosphonate functionalized ligands as anticancer organometallics
Harringer, Sophia,Hejl, Michaela,Jakupec, Michael A.,Kandioller, Wolfgang,Keppler, Bernhard K.,Riedl, Christoph A.,Rosner, Alexander,Salomon, Philipp
, (2021/10/04)
Trithiolato-bridged dinuclear ruthenium(II) complexes [Ru2(p-cym)2(SR)3]Cl (p-cym = p-cymene, R = benzyl derivatives) are regarded as the most cytotoxically potent metal(II) arene antineoplastics, but are oftentimes limited by their poor solubility in aqueous media. Thus, we designed bisphosphonate-functionalized ligands for use in a modular two-step complexation process to synthesize six trithiolato-bridged dinuclear ruthenium(II) and osmium(II) arene complexes bearing one to three bisphosphonate-benzylmercaptane derived ligands. In addition to improved aqueous solubility the high affinity of bisphosphonates towards apatite structures found in bone and bone metastases may grant selective targeting properties to functionalized organometallics. The complex stabilities and hydroxyapatite binding behavior were determined by UV/Vis spectroscopy. The bisphosphonate functionalization decreases antiproliferative activity in vitro, which was correlated to lower cellular accumulation, due to the different lipophilic profiles of the drug candidates.
