ABSTRACT
Access to C,C-glycosyl amino acids as a novel class of glycomimetics is reported by means of radical generation, intermolecular addition and stereoselective reduction via a metal-induced hydrogen atom transfer (MHAT) sequence. The 'matched' coupling of exo-D-glycals with an enantiopure dehydroalanine bearing a (R)-configured benzyl oxazolidinone enables a singular case of two-fold diastereocontrol under iron catalysis. In the common exo-D-glucal series, the nature of the C-2 substituent was found to play a key role from both reactivity and stereocontrol aspects.
ABSTRACT
The stereodefined construction of quaternary pseudoanomeric centers by way of a BF3·Et2O-catalyzed, Fries-type rearrangement of O-ketosides is described. This method provides new access to C-naphthyl ketosides related to biologically relevant products with good to complete stereocontrol in favor of the ß product.
ABSTRACT
Lignocellulosic fibres modification focused so far essentially on the resulting material properties to create functional fibres instead of determining the reaction influencing parameters. Using a data-mining algorithm, surface chemical composition of the fibres after modifications was compared to multiple signals. A 24 h reaction at either 25 °C or 60 °C, pH5 was conducted in presence of trans-ferulic acid, laccase, and lignocellulosic fibres (flax, hemp, or cellulose) having different chemical surface composition. Dimers and trimers were detected in variable concentrations in the reaction filtrate and extractive. At 25 °C, crystalline cellulose, amorphous cellulose, xylans, mannans, and lignins were well correlated to specific reaction products while at 60 °C, only lignins and xylan were found correlated to reaction products. Fibres surface composition affected the extractive profile. Lignocellulosic surface composition influence on the product formed was unveiled using a data mining approach. This study presents a way to unveil non-evident chemical interface interaction in reactions.
