Oxidative Depolymerization of Alkaline Lignin from Pinus Pinaster by Oxygen and Air for Value-Added Bio-Sourced Synthons.

In this work, an efficient 3-step process targeting the chemical modification and purification of lignin oligomers from industrial alkaline lignin is described. The oxidative depolymerization process of alkaline lignin with O2 or Air pressure, without use of metal catalyst, led to the production of two fractions of lignin oligomers named 'precipitated lignin' and 'hydrosoluble lignin' with 40% and 60% yield, respectively. These fractions were characterized with a wide range of methods including NMR spectroscopy (31P, 2D-HSQC), SEC (in basic media), FTIR. NMR analyses revealed the presence of carboxylic acid functions at a ratio of 1.80 mmol/g and 2.80 mmol/g for the precipitated and hydrosoluble lignin, respectively, values much higher than what is generally found in native lignin (between 0.2 and 0.5 mmol/g). SEC analyses revealed the formation of low molar masses for the precipitated (2200 g/mol) and hydrosoluble fractions (1500 g/mol) in contrast to the alkaline lignin (3900 g/mol). It is worth noting that the hydrosoluble fraction of lignin is soluble in water at any pH. Both processes (oxygen and air) were successfully scaled up and showed similar results in terms of yield and functionalization.

Extraction and Characterization of Hemicelluloses from a Softwood Acid Sulfite Pulp.

Hemicelluloses were extracted from a softwood acid sulfite pulp in a three-step procedure. Further delignification step resulted in a holocellulose pulp containing only 1.7 wt.% of the lignin left. Cold caustic extraction (CCE) with 18 wt.% NaOH at 60 °C for 1 h was performed to solubilize hemicelluloses of the holocellulose. An unbleached cellulose pulp was then obtained 97% pure, which indicates that 89% of the hemicelluloses were removed. After purification, extraction yields between 1.1 wt.% and 9.5 wt.% were obtained from the delignified pulp and the hemicelluloses' chemical compositions and structures were investigated by 1H, 13C nuclear magnetic resonance spectroscopy (NMR) and two-dimensional NMR by correlation spectroscopy (2D-COSY) and proton-detected heteronuclear single-quantum correlation (2D-HSQC), high-performance anion-exchange chromatography coupled with a pulsed amperometry detector (HPAEC-PAD), size-exclusion chromatography coupled with a refractive index detector (SEC-RI) and thermogravimetric analyses (TGA). Hemicelluloses were obtained with a purity of 96%, with short cellulosic chains as the only residue. Sulfite pulping modified the hemicelluloses' structure, and it was found that two types of hemicelluloses were isolated, glucomannans, predominant at 67%, and methylglucuronoxylans. Finally, alkali-soluble hemicelluloses displayed relatively narrow size distributions and low molar masses, Mw varying between 18,900 and 30,000 g/mol after acid sulfite pulping.

Intramolecular homolytic substitution of sulfinates and sulfinamides.

A general and efficient method for the synthesis of cyclic sulfinates and sulfinamides based on intramolecular homolytic substitution (S(H)i) at the sulfur atom by aryl or alkyl radicals is described. Both alkyl and benzofused compounds can be accessed directly from easily prepared acyclic precursors. Enantiomerically enriched sulfur-based heterocycles were formed through an S(H)i process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2-Pyridyl and 2-quinolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.

Second generation N-heterocyclic carbene-Pt(0) complexes as efficient catalysts for the hydrosilylation of alkenes.

A new class of benzimidazolylidene carbene-Pt(0) complexes was developed and used to efficiently catalyse the hydrosilylation of alkenes.

A Stable (Amino)(Phosphino)Carbene as bidentate ligand for Palladium and Nickel Complexes: Synthesis, Structure, and Catalytic Activity.

Two original complexes featuring an (amino)(phosphino)carbene η(2)-bonded to the metal have been obtained in 60 and 80 % yields, by addition of the corresponding stable carbene to PdCl(2)(cod) and NiCl(2)(PPh(3))(2), respectively. Both complexes have been fully characterized including X-ray diffraction studies. The catalytic activity of the palladium complex has been evaluated for aryl amination reactions.

Selective and efficient platinum(0)-carbene complexes as hydrosilylation catalysts.

The hydrosilylation reaction enables the production of silicon polymers. Platinum-carbene complexes are reported that catalyze the hydrosilylation reaction of alkenes with remarkable efficiency and exquisite selectivity and avoid the formation of platinum colloids. By-products, typically encountered with previous catalytic systems, are suppressed with these platinum derivatives.

Platinum oxide (PtO(2)): a potent hydrosilylation catalyst.

[reaction: see text] Platinum oxide was found to be a versatile and powerful hydrosilylation catalyst upon a wide variety of functionalized alkenes and especially aminated alkenes. Moreover, highly reproducible results and easy removal make this new catalyst a useful tool for hydrosilylation reaction.