Ketoxime ethers at C3 of 1,6-anhydro-beta-D-mannopyranose derivatives were found to be useful 5-exo radical traps of alkyl and vinyl radicals generated at a chain tethered to the C2 hydroxyl group, allowing advanced synthetic intermediates for (-)-tetrodotoxin to be prepared from D-mannose in good overall yield.

The 1,3-dipolar cycloaddition of sugar ketonitrones is a useful synthetic procedure to build up nitrogenated quaternary centers in terms of scope (substrate, dipolarophile, inter- and intramolecular versions), yield, and regio- and stereoselectivity. The hybrid ONIOM (B3LYP/6-31G(d):AM1) theoretical method followed by single-point energy calculations at the B3LYP/6-31G(d) level adequately perform to model this cycloaddition for the relatively large ketosugar precursors commonly used.

No abstract

No abstract