SYNTHESIS OF CHIRAL γ-AMINO-YNAMIDES USING LITHIATED YNAMIDES. OBSERVATION OF A UNIQUE 5- CYCLIZATION WITH AN INVERSION OF -CENTER.

We describe herein details of our efforts in developing a highly stereoselective synthesis of de chiral γ-amino-ynamides through additions of lithiated ynamides to Ellman-Davis chiral -butanesulfinyl imines. While additions of ynamides could be highly stereoselective even without Lewis acids, the use of BF-OEt completely reversed the stereoselectivity. On the other hand, additions of oxazolidinone-substituted, oxazinanone-substituted and tetrahydropyrimidinone-substituted ynamides behaved quite differently and functioned better with BF-OEt. The chirality of the oxazolidinone ring exerts no impact on the selectivity. This work also features a unique 5- cyclization of oxazolidinone-substituted γ-amino-ynamides that could be promoted with acid, leading to isothiazoles and 2,3-dihydro-isothiazole -oxides.