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- ItemSynthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks(London : Soc., 2015) Bresien, Jonas; Faust, Kirill; Hering-Junghans, Christian; Rothe, Julia; Schulz, Axel; Villinger, AlexanderDifferent reactions of Mes* substituted phosphanes (Mes* = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes*P4Mes* (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo–exo isomer of 5 was fully characterized for the first time. The synthesis was achieved by reactions involving “self-assembly” of the P4 scaffold from P1 building blocks (i.e. primary phosphanes) or by reactions starting from P2 or P4 scaffolds (i.e. a diphosphene or cyclic tetraphosphane). Furthermore, interconversion between the exo–exo and endo–exo isomer were studied by 31P NMR spectroscopy. All compounds were fully characterized by experimental as well as computational methods.
- ItemBio-based building blocks from 5-hydroxymethylfurfural via 1-hydroxyhexane-2,5-dione as intermediate(Cambridge : RSC, 2019) Wozniak, Bartosz; Tin, Sergey; de Vries, Johannes G.The limits to the supply of fossil resources and their ever increasing use forces us to think about future scenarios for fuels and chemicals. The platform chemical 5-hydroxymethyl-furfural (HMF) can be obtained from biomass in good yield and has the potential to be converted in just a few steps into a multitude of interesting products. Over the last 20 years, the conversion of HMF to 1-hydroxyhexane-2,5-dione (HHD) has been studied by several groups. It is possible to convert HMF into HHD by hydrogenation/hydrolytic ring opening reaction in aqueous phase using various heterogeneous and homogeneous catalysts. This review addresses both the state of the art of HHD synthesis, including mechanistic aspects of its formation, as well as the recent progress in the application of HHD as a building block for many useful chemicals including pyrroles, cyclopentanone derivatives and triols. © 2019 The Royal Society of Chemistry.
- ItemThe Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors(Washington, DC : ACS Publications, 2015) Smith, Dan A.; Beweries, Torsten; Blasius, Clemens; Jasim, Naseralla; Nazir, Ruqia; Nazir, Sadia; Robertson, Craig C.; Whitwood, Adrian C.; Hunter, Christopher A.; Brammer, Lee; Perutz, Robin N.The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (−23.5 ± 0.3 kJ mol–1) interlocks our study with Laurence’s scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ–dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.
- ItemIndirect reduction of CO2 and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes(Cambridge : RSC, 2021) Liu, Xin; Werner, ThomasThe reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed. © The Royal Society of Chemistry 2021.
- ItemScreening Libraries of Amphiphilic Janus Dendrimers Based on Natural Phenolic Acids to Discover Monodisperse Unilamellar Dendrimersomes(Columbus, Ohio : American Chemical Society, 2019) Buzzacchera, Irene; Xiao, Qi; Han, Hong; Rahimi, Khosrow; Li, Shangda; Kostina, Nina Yu; Toebes, B. Jelle; Wilner, Samantha E.; Möller, Martin; Rodriguez-Emmenegger, Cesar; Baumgart, Tobias; Wilson, Daniela A.; Wilson, Christopher J.; Klein, Michael L.; Percec, VirgilNatural, including plant, and synthetic phenolic acids are employed as building blocks for the synthesis of constitutional isomeric libraries of self-assembling dendrons and dendrimers that are the simplest examples of programmed synthetic macromolecules. Amphiphilic Janus dendrimers are synthesized from a diversity of building blocks including natural phenolic acids. They self-assemble in water or buffer into vesicular dendrimersomes employed as biological membrane mimics, hybrid and synthetic cells. These dendrimersomes are predominantly uni- or multilamellar vesicles with size and polydispersity that is predicted by their primary structure. However, in numerous cases, unilamellar dendrimersomes completely free of multilamellar assemblies are desirable. Here, we report the synthesis and structural analysis of a library containing 13 amphiphilic Janus dendrimers containing linear and branched alkyl chains on their hydrophobic part. They were prepared by an optimized iterative modular synthesis starting from natural phenolic acids. Monodisperse dendrimersomes were prepared by injection and giant polydisperse by hydration. Both were structurally characterized to select the molecular design principles that provide unilamellar dendrimersomes in higher yields and shorter reaction times than under previously used reaction conditions. These dendrimersomes are expected to provide important tools for synthetic cell biology, encapsulation, and delivery.
- ItemMixed-halide triphenyl methyl radicals for site-selective functionalization and polymerization(London : RSC Publishing, 2021) Chen, Lisa; Arnold, Mona; Blinder, Rémi; Jelezko, Fedor; Kuehne, Alexander J. C.Derivatives of the stable, luminescent tris-2,4,6-trichlorophenylmethyl (TTM) radical exhibit unique doublet spin properties that are of interest for applications in optoelectronics, spintronics, and energy storage. However, poor reactivity of the chloride-moieties limits the yield of functionalization and thus the accessible variety of high performance luminescent radicals. Here, we present a pathway to obtain mixed-bromide and chloride derivatives of TTM by simple Friedel–Crafts alkylation. The resulting radical compounds show higher stability and site-specific reactivity in cross-coupling reactions, due to the better leaving group character of the para-bromide. The mixed halide radicals give access to complex, and so far inaccessible luminescent open-shell small molecules, as well as polymers carrying the radical centers in their backbone. The new mixed-halide triphenyl methyl radicals represent a powerful building block for customized design and synthesis of stable luminescent radicals.