María I. Mangione

Cellulose recycling as a source of raw chirality

Modern organic chemistry requires easily obtainable chiral building blocks that show high chemical versatility for their application in the synthesis of enantiopure compounds. Biomass has been demonstrated to be a widely available raw material that represents the only abundant source of renewable organic carbon. Through the pyrolitic conversion of cellulose or cellulose-containing materials it is possible to produce levoglucosenone, a highly functionalized chiral structure. This compound has been innovatively used as a template for the synthesis of key intermediates of biologically active products and for the preparation of chiral auxiliaries, catalysts, and organocatalysts for their application in asymmetric synthesis.

Experimental and theoretical study of a Diels–Alder reaction between a sugar-derived nitroalkene and cyclopentadiene

The Diels-Alder reaction of a pyranose-derived nitroalkene 1 with cyclopentadiene is described, and the unexpected facial selectivity of the cycloaddition is analyzed by a computational study.

Neighboring-group participation in benzylidene acetal ring-opening of a 2-cyano-2-deoxypyranoside derivative by diethylaluminum cyanide

The oxirane ring-opening of an anhydro sugar with diethylaluminum cyanide (Et(2)AlCN) is a direct approach for obtaining a cyano derivative. Methyl 2,3-anhydro-4,6-O-benzylidene-alpha-D-allopyranoside showed anomalous chemical behavior when treated with Et(2)AlCN. The reaction afforded the corresponding beta-cyanohydrin as the minor component from a mixture of compounds resulting from the benzylidene acetal ring-opening caused by the attack of ethyl or cyano groups.

Synthesis of a 3-Thiomannoside

An efficient and straightforward synthesis of a novel 3-thiomannoside derivative (1,2,4,6-tetra-O-acetyl-3-S-acetyl-3-thio-β-d-mannopyranoside) was developed starting from levoglucosenone. A xanthate-thiocarbonate exchange under acidic conditions was the key step for the new C-S bond. The product was obtained enantiospecifically in very good overall yield.