Pd-catalyzed asymmetric intermolecular hydroalkoxylation of allene: an entry to cyclic acetals with activating group-free and flexible anomeric control.

A ligand-directed metal-catalyzed asymmetric intermolecular hydroalkoxylation of alkoxyallene is reported. Combined with ring-closing-metathesis, this reaction offers a new atom-efficient synthetic method toward various cyclic acetals with elaborate anomeric control. Synthetic utility of the reaction was demonstrated by the atom-efficient and stereodivergent access to various mono- and disaccharides.

Gold(I)-catalyzed synthesis of γ-hydroxyketones from 5-allyloxy-1-ynes.

The Au(I)-catalyzed reactions of 5-allyloxy-1-ynes gave various γ-hydroxyketones, via a hydration-terminated domino sequence involving sigmatropic allyl migration as the key event. Moreover, the scope of the sigmatropic allyl transfer was systematically determined.