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Updated: Apr 30, 2026

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine
Published on: June 13, 2022
SYNTHESIS OF DE NOVO CHIRAL γ-AMINO-YNAMIDES USING LITHIATED YNAMIDES. OBSERVATION OF A UNIQUE 5-ENDO-DIG CYCLIZATION
Xiao-Na Wang1, Richard P Hsung1, Sierra K Fox1
1Division of Pharmaceutical Sciences, School of Pharmacy, and Department of Chemistry, University of Wisconsin, Madison, WI 53705, USA.
Abstract:
We describe herein details of our efforts in developing a highly stereoselective synthesis of de novo chiral γ-amino-ynamides through additions of lithiated ynamides to Ellman-Davis chiral N-tert-butanesulfinyl imines. While additions of ynamides could be highly stereoselective even without Lewis acids, the use of BF3-OEt2 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 BF3-OEt2. The chirality of the oxazolidinone ring exerts no impact on the selectivity. This work also features a unique 5-endo-dig cyclization of oxazolidinone-substituted γ-amino-ynamides that could be promoted with acid, leading to isothiazoles and 2,3-dihydro-isothiazole S-oxides.
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