Studies on the hydrogenation of 6-(hydroxymethyl)pyridine-2-carboxylates and its application to the synthesis of 6-(hydroxymethyl)piperidine-2-carboxylic acid derivatives

The synthesis of the novel amino acid 6-(hydroxymethyl)-2-piperidinecarboxylic acid ( 1a ) and its ethyl ester 1b is reported. In the hydrogenation of 6-(hydroxymethyl)pyridine-2-carboxylates, hydrogenolysis of the alcohol group appeared as an unusual side reaction. Optimization of the reaction conditions allowed us to minimize hydrogenolysis and afforded pure 1 .     

Solution structures by NMR of a novel antifungal drug: Petriellin A

Petriellin A is a novel cyclic depsipeptide antifungal compound consisting of nine l-configured residues, one d-phenyllactic acid (PhLac) and three unknown chiral centres: two N-methyl-threonines (MeThr1 & MeThr2) and one N-methyl-isoleucine (MeIle). NMR experiments including 2D ROESY, NOESY along with structural and energy calculations predicted that the unknown chiral centres were all l-configured, which was later verified chemically. Simulated annealing, dynamics calculations and minimisation processes showed Petriellin A to have a folded "C-shaped" structure.     

Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures.     

Hooking Together Sigmoidal Monomers into Supramolecular Polymers

Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.     

Stereoselective RhI-catalyzed tandem conjugate addition of boronic acids-Michael cyclization

The first examples of the stereoselective sequence RhI-catalyzed tandem conjugate addition of boronic acids to enones-Michael cyclization, is reported. The reaction is carried out in dioxane-H2O at rt, and 1,2,3-trisubstituted indans are obtained in a highly regio- and stereoselective fashion.     

Open-pore biodegradable foams prepared via gas foaming and microparticulate templating

Open-pore biodegradable foams with controlled porous architectures were prepared by combining gas foaming and microparticulate templating. Microparticulate composites of poly(epsilon-caprolactone) (PCL) and micrometric sodium chloride particles (NaCl), in concentrations ranging from 70/30 to 20/80 wt.-% of PCL/NaCl were melt-mixed and gas-foamed using carbon dioxide as physical blowing agent. The effects of microparticle concentration, foaming temperature, and pressure drop rate on foam microstructure were surveyed and related to the viscoelastic properties of the polymer/microparticle composite melt. Results showed that foams with open-pore networks can be obtained and that porosity, pore size, and interconnectivity may be finely modulated by optimizing the processing parameters. Furthermore, the ability to obtain a spatial gradient of porosity embossed within the three-dimensional polymer structure was exploited by using a heterogeneous microparticle filling. Results indicated that by foaming composites with microparticle concentration gradients, it was also possible to control the porosity and pore-size spatial distribution of the open-pore PCL foams.     

Theoretical study of oligomeric alumatranes present in the chemistry of materials from micro to mesoporous molecular sieves and alumina composites

Quantum chemical calculations using density functional theory have been carried out to investigate molecular precursors based on alumatranes which are one of the components with silatranes for the preparation of mesoporous aluminosilicate materials. In the same way, some oligomeric alumatranes of this study take part in chemical syntheses related to materials such as zeolites and alumina composite. Gas phase and solution equilibrium geometries of the alumatrane precursors were fully optimized at B3LYP level, modeling solvent effects using a self-consistent reaction field (SCRF). From these optimized geometries, calculations of the ¹H, ¹³C and ²⁷Al NMR chemical shifts at GIAO/B3LYP/6-31G(d,p) levels of theory have also been performed. This study has shown that the assumed conformations of the alumatrane precursors that have been derived from a previous work on a FAB-MASS analysis (Fast Atomic Bombardment Mass Spectroscopy) are confirmed by DFT calculations. All the conformations of alumatranes show that there would have transannular Al–N bond. Oligomeric alumatranes are composed of one or more two-membered Al₂O₂ rings where tricoordinated oxygen would be present. A good agreement between the experimental NMR data and the theoretical study on the chemical shifts of nucleus as ¹³C, ¹H and ²⁷Al from full geometry optimizations of the alumatrane precursors seems to corroborate the presence of the alumatrane precursors in the “atrane route”.     

Phosphine Oxide-Functionalized Terthiophene Redox Systems

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e⁻ reductions at potentials below −2 V vs Fc/Fc⁺ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e⁻ galvanostatic charge–discharge cycling and enabled characterization of a 2 e⁻ redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.