Christopher T. Burns

Stereoselective acetylation of hemicellulosic C5-sugars

The stereoselective peracetylation of α-d-xylose (1) and α-l-arabinose (4) using a combination of triethylamine and acetic anhydride in the presence or absence of a catalytic amount of dimethylaminopyridine (DMAP) is described. The peracetylated d-xylose and l-arabinose alpha pyranose anomers 2α and 5α are obtained in 97% and 56% yields respectively. The peracetylated d-xylose beta pyranose anomer 2β is obtained in 71% yield through simple modification of the reaction conditions. Details regarding synthesis and isolation optimization studies under different conditions are presented below. The stereoselective peracetylation reactions disclosed here have been used to separate mixtures of d-xylose and l-arabinose as their peracetylated derivatives 2β and 5α in 47% and 42% yields and can provide pure pentoses after deacetylation.

2-[(Di-methyl-phenyl-phosphanyl-idene)aza-nium-yl]-5-methyl-benzene-sulfonate benzene monosolvate.

The title compound, C15H18NO3PS·C6H6, is a rare example of a crystallographically characterized exocyclic phosphiniminium–arenesulfonate zwitterion, which crystallises as its benzene solvate. The crystal structure shows that the N atom is protonated and that the iminium H atom forms both intra- and intermolecular hydrogen bonds to the single-bonded sulfonate O atom in an R 2 2(4) graph-set motif. The dihedral angle between the aromatic rings in the main molecule is 89.49 (8)°.