Can Coordination‐Driven Supramolecular Self‐Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

The reaction between a preassembled Cu^I bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano‐capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano‐capped linkers with two other types of preassembled Cu^I bimetallic molecular clips that also had short intermetallic distances.     

Asymmetric synthesis and structure-activity studies of the fungal metabolites colletorin A,colletochlorin A and their halogenates analogues

The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature.     

A decanuclear oxomolybdenum(V,VI) cluster with 4-isopropylpyridine

The title centrosymmetric cluster octakis(4-iso­propyl­pyridine-N)-di-μ₄-oxo-hexa-μ₃-oxo-octa-μ₂-oxo-deca­oxo­octa­molyb­denum(V)­dimolybdenum(VI), [Mo₁₀O₂₆(C₈H₁₁N)₈], consists of ten Mo atoms connected together by bridging oxo groups. Pentavalent Mo atoms are linked into four Mo₂^V pairs by metal–metal single bonds with lengths of 2.5637 (6) and 2.6132 (6) Å.     

Surface and bulk modification of polyolefins by functional aryl nitrenes as highly reactive intermediates

Aromatic azides with hindered amine light stabilizer (HALS) residues or hydrophilic groups such as glucose, sucrose and dextrine residues were synthesized and used for surface modification of polyolefins. By UV‐irradiation nitrenes were formed, which are able to react with polyolefin surfaces. By photochemical immobilization of the carbohydrates hydrophilicity of PE and PP was strongly increased (surface tensions > 44mN/m). Light stability of PP surfaces modified with HALS azides was comparable with PP, stabilised with Tinuvin 770. Bulk modification of ethylene‐propylene and ethylene‐octene copolymers was achieved by grafting nitrenes formed by thermal decomposition of azido benzoic acid. In a circulating air oven up to 1.55 wt% amino benzoic acid residues could be bonded covalently to ethylene‐propylene‐copolymers, less than half of it to ethylene‐octene‐copolymers. Reactive extrusion resulted in grafting yields of more than 50% for both types of copolymers.     

Die Struktur des Pentaphenyldisilans

Structure of Pentaphenyldisilane For the first time Pentaphenyldisilane was prepared by Gilman and Goodman. It is produced by the reaction of Ph₃SiLi with Ph₂ClSiH. The crystal structure presents an ideally staggered conformation. The distance d(Si? Si) = 235.7 pm corresponds to a normal single bond length. This emphasizes the complete relief of the central Si? Si bond by the insertion of only one hydrogen atom.     

Temperature-controlled 'breathing' of carbon dioxide bubbles

We report a microfluidic (MF) approach to studies of temperature mediated carbon dioxide (CO(2)) transfer between the gas and the liquid phases. Micrometre-diameter CO(2) bubbles with a narrow size distribution were generated in an aqueous or organic liquid and subsequently were subjected to temperature changes in the downstream channel. In response to the cooling-heating-cooling cycle the bubbles underwent corresponding contraction-expansion-contraction transitions, which we term 'bubble breathing'. We examined temperature-controlled dissolution of CO(2) in four exemplary liquid systems: deionized water, a 0.7 M aqueous solution of NaCl, ocean water extracted from Bermuda coastal waters, and dimethyl ether of poly(ethylene glycol), a solvent used in industry for absorption of CO(2). The MF approach can be extended to studies of other gases with a distinct, temperature-dependent solubility in liquids.     

The study of the lipophilicity of alpha-(4-phenylpiperazin-1-yl)-gamma-phthalimidobutyramides using chromatographic and computational methods

The lipophilicity of the series of alpha-(4-phenylpiperazin-1-yl)-gamma-phthalimido-butyramides (1-8) has been investigated. Several methods, like reversed-phase thin-layer chromatography and high-performance liquid chromatography using reversed-phase RP18 and IAM.DD2 columns, were applied to determine RMO, log k0 and log k(0IAM) factors. The RP-TLC investigations were performed in mixtures of acetone-water and acetonitrile-water. For RP-HPLC method mixtures of acetonitrile, water and 0.01% TFA were used as the mobile phases while for IAM.DD2 investigations mixtures of acetonitrile and water were applied. The partition coefficients of compounds (1-8) were also calculated with the Pallas and CAChe programs. All the obtained data, both from experimental methods and computational calculations, were compared and a suitable conclusion was reached.     

Predictable Selectivity in Remote C−H Oxidation of Steroids: Analysis of Substrate Binding Mode

Predictability is a key requirement to encompass late‐stage C?H functionalization in synthetic routes. However, prediction (and control) of reaction selectivity is usually challenging, especially for complex substrate structures and elusive transformations such as remote C(sp³)?H oxidation, as it requires distinguishing a specific C?H bond from many others with similar reactivity. Developed here is a strategy for predictable, remote C?H oxidation that entails substrate binding to a supramolecular Mn or Fe catalyst followed by elucidation of the conformation of the host‐guest adduct by NMR analysis. These analyses indicate which remote C?H bonds are suitably oriented for the oxidation before carrying out the reaction, enabling prediction of site selectivity. This strategy was applied to late‐stage C(sp³)?H oxidation of amino‐steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal.