Synthesis of chiral azides from C-2 substituted glycals and their transformation to C3-glycoconjugates and α-triazolo-naphthalene polyol.

A Lewis-acid-mediated highly regio- and stereoselective chiral azidation of C2-substituted glycals is reported. This strategy provides excellent, scalable, and mild reaction conditions for the stereoselective introduction of the azido group at the C3-position of various C2-substituted glycals. The reactivity of the various glycals reveals that the electron-withdrawing behavior of the C2-group is crucial for C3-selectivity.

Pd-catalyzed direct functionalization of glycals with cycloalkenones: application to the synthesis of chiral phenanthrenones.

A palladium-catalyzed direct C-H functionalization of glycals with cycloalkenones is described and a series of C-2 functionalized glycals were synthesized efficiently with cyclic enones. The direct C-H functionalization of glycals with Pd(II) and subsequent insertion of cyclic enones β-hydride elimination is the key to the synthesis of 2C-branched glycals. The synthetic utility of this methodology for chiral phenanthrenones has also been demonstrated by coupling the synthesized 2C-branched glycals with arynes 4+2 cycloaddition followed by concomitant pyran ring opening.