Synthesis of Propargylamines via Michael Addition Using Methyl Vinyl Ketone Derivatives, 1-Alkynes, and Secondary Amines Catalyzed by Copper (I) Halides.

Propargylamines are synthesized from methyl vinyl ketone derivatives, 1-alkynes, and secondary amines catalyzed by Cu salts involving the Michael addition of amine followed by an unusual C-C bond cleavage and addition of metal acetylides formed in situ to iminium ions. In this approach, the di-, tri-, and tetrasubstituted propargylamines are synthesized in 46-98% yields.

Enantioselective Synthesis of β-Allenoates via Phosphine-Catalyzed and ZnI-Promoted Preparation of Oxazolidines and Propargylamines Using Chiral Amines, 1-Alkynes, and Propiolates.

Diphenylphosphinoethane (DPPE)-catalyzed and ZnI-promoted in situ formation of oxazolidine, alkynyl zinc, and propargylamine intermediates from 1-alkynes, chiral (S)-diphenyl(pyrrolidin-2-yl)methanol, and propiolates gave the corresponding chiral (R)-β-allenoates in 40-72% yield with up to >99% ee. The intermediate propargylamine was isolated in 50% yield and converted to give the β-allenoate 10aa in 68% yield and 96% ee upon reaction with ZnI. The results are discussed considering a mechanism involving oxazolidine and iminium ions formed in situ followed by addition of alkynyl zinc complex to produce the propargylamine that gives the corresponding allenoate via a 1,5-hydrogen shift in the presence of ZnI.