Brønsted-Acid-Catalyzed Enantioselective Desymmetrization of 1,3-Diols: Access to Chiral ß-Amino Alcohol Derivatives.

Herein, we describe a Brønsted-acid-catalyzed enantioselective desymmetrization of 1,3-diols with alkynes through a hydroalkoxylation/hydrolysis process. The reaction leads to the atom-economical synthesis of valuable chiral ß-amino alcohols under mild reaction conditions. Further synthetic transformations based on the ß-amino alcohol moiety provide divergent approaches toward chiral N-containing heterocycles.

Copper-Catalyzed Si-H Bond Insertion Reaction of N-Propargyl Ynamides with Hydrosilanes.

Transition-metal-catalyzed Si-H bond insertion reactions are generally limited to stabilized diazo compounds. An efficient copper-catalyzed Si-H bond insertion reaction of N-propargyl ynamides with hydrosilanes is described, allowing practical and atom-economic construction of valuable organosilanes in generally moderate to excellent yields under mild reaction conditions. Notably, this reaction constitutes a new method of Si-H bond insertion reaction involving vinyl cations as key intermediates.