Carbon Dioxide as a Protecting Group: Highly Efficient and Selective Catalytic Access to Cyclic cis‐Diol Scaffolds

The efficient and highly selective formation of a wide range of (hetero)cyclic cis‐diol scaffolds using aminotriphenolate‐based metal catalysts is reported. The key intermediates are cyclic carbonates, which are obtained in high yield and with high levels of diastereo‐ and chemoselectivity from the parent oxirane precursors and carbon dioxide. Deprotection of the carbonate structures affords synthetically useful cis‐diol scaffolds with different ring sizes that incorporate various functional groups. This atom‐efficient method allows the simple construction of diol synthons using inexpensive and accessible precursors and green metal catalysts and showcases the use of CO₂ as a temporary protecting group.     

A ‘waterproof’ catalyst for the oxidation of secondary amines to nitrones with alkyl hydroperoxides

Catalytic oxidation of secondary amines to nitrones using alkyl hydroperoxides as primary oxidant has been demonstrated for the first time. The titanium alkoxide catalyst is protected from co-product water by the combined use of a tightly binding trialkanolamine ligand and molecular sieves. Nitrones can be obtained in high yield (up to 98%) under homogeneous, anhydrous conditions and even in the absence of solvent. The reactions are fast (2-7 h) and good selectivity can be achieved with as little as 1% catalyst.     

Proteomic analysis of a spring wheat cultivar in response to prolonged cold stress

Cold represents one of the major abiotic factors influencing plant growth and development worldwide. We analysed the long-term responsiveness of an Iranian spring wheat (cv. Kohdasht) to cold from a proteomic point of view, in order to unravel the molecular mechanisms helping a cold-sensitive cultivar to survive exposure to suboptimal temperatures. Plants were grown at 20 or 4°C until entering the reproductive stage and a cross-comparison on the leaf proteomes was performed. Quantitative analyses on protein alterations occurring upon low-temperature exposure showed a reinforcement in ascorbate recycling (dehydroascorbate reductase, ascorbate peroxidase) and protein processing (proteasome subunit, cysteine proteinase), as well as the accumulation of the enzyme devoted to tetrapyrrole resynthesis (glutamate semialdehyde aminomutase). In contrast, among proteins down-regulated after cold stress, we could identify some key Krebs cycle enzymes (isocitrate dehydrogenase, malate dehydrogenase), together with many photosynthesis-related proteins (oxygen-evolving complex proteins, ATP synthase subunits, ferredoxin NADPH oxidoreductase and some Calvin cycle enzymes). Physiological and biochemical parameters (such as shoot apex dissection, chlorophyll, proline and sugar content determination) sustained proteomics findings allowing the present research to contribute to the current knowledge on these long-term responses, which may be crucial to stress adaptation under field conditions.     

HMGB1–Carbenoxolone Interactions: Dynamics Insights from Combined Nuclear Magnetic Resonance and Molecular Dynamics

The interplay of protein dynamics and molecular recognition is of fundamental importance in biological processes. Atomic‐resolution insights into these phenomena may provide new opportunities for drug discovery. Herein, we have combined NMR relaxation experiments and residual dipolar coupling (RDC) measurements with molecular dynamics (MD) simulations to study the effects of the anti‐inflammatory drug carbenoxolone (CBNX) on the conformational properties and on the internal dynamics of a subdomain (box A) of high‐mobility group B protein (HMGB1). ¹⁵N relaxation data show that CBNX binding enhances the fast pico‐ to nanosecond motions of a loop and partially removes the internal motional anisotropy of the first two helices of box A. Dipolar wave analysis of amide RDC data shows that ligand binding induces helical distortions. In parallel, increased mobility of the loop upon ligand binding is highlighted by the essential dynamics analysis (EDA) of MD simulations. Moreover, simulations detect two possible orientations for CBNX, which induces two possible conformations of helix H3, one being similar to the free form and the second one causing a partial helical distortion. Finally, we introduce a new approach for the analysis of the internal coordination of protein residues that is consistent with experimental data and allows us to pinpoint which substructures of box A are dynamically affected by CBNX. The observations reported here may be useful for understanding the role of protein dynamics in binding at atomic resolution.     

A Flexible Pro‐porous Coordination Polymer: Non‐conventional Synthesis and Separation Properties Towards CO2/CH4 Mixtures

The novel coordination polymers [Cu(Hoxonic)(H₂O)]_n ( 1 ) and [Cu(Hoxonic)(bpy)_0.5]_n ? 1.5 n H₂O ( 2?H₂O ) (H₃oxonic: 4,6‐dihydroxy‐1,3,5‐triazine‐2‐carboxylic acid; bpy: 4,4′‐bipyridine) have been isolated and structurally characterised by ab initio X‐ray powder diffraction. The dense phase 1 contains 1D zig‐zag chains in which Hoxonic dianions bridge square‐pyramidal copper(II) ions, apically coordinated by water molecules. On the contrary, 2?H₂O , prepared by solution and solventless methods, is based on 2D layers of octahedral copper(II) ions bridged by Hoxonic ligands, further pillared by bpy spacers. The resulting pro‐porous 3D network possesses small hydrated cavities. The reactivity, thermal, magnetic and adsorptive properties of these materials have been investigated. Notably, the adsorption studies on 2 show that this material possesses unusual adsorption behaviour. Indeed, guest uptake is facilitated by increasing the thermal energy of both the guest and the framework. Thus, neither N₂ at 77 K nor CO₂ at 195 K are incorporated, and CH₄ is only minimally adsorbed at 273 K and high pressures (0.5 mmol g^?1 at 2500 kPa). By contrast, CO₂ is readily incorporated at 273 K (up to 2.5 mmol g^?1 at 2500 kPa). The selectivity of 2 towards CO₂ over CH₄ has been investigated by means of variable‐temperature zero coverage adsorption experiments and measurement of breakthrough curves of CO₂/CH₄ mixtures. The results show the highly selective incorporation of CO₂ in 2 , which can be rationalised on the basis of the framework flexibility and polar nature of its voids.     

Stereoselective Control by Face‐to‐Face Versus Edge‐to‐Face Aromatic Interactions: The Case of C3‐TiIV Amino Trialkolate Sulfoxidation Catalysts

The stereoselective oxidation of differently functionalised benzyl phenyl sulfides has been examined by using enantiopure Ti^IV trialkanolamine complexes. These complexes efficiently catalyse the sulfoxidation with good stereoselectivities. The data highlight the contribution to the stereoselectivity of steric effects and non‐covalent π–π interactions between the aromatic rings of the Ti^IV complex and those pertaining to the substrates. Enantiomeric excesses have been correlated with the electrostatic potential surfaces (EPS) of the reacting sulfides. The overall study leads to a mechanistic interpretation that explains the stereoselectivity of the system and dissects the role of aromatic and steric interactions in the stereoselective process.     

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.