Ligand-Enabled Palladium-Catalyzed Asymmetric Synthesis of Cyclic Sulfamidate-Fused Imidazolidinones

Both cyclic sulfamidates and imidazolidinones own diverse biological and pharmaceutical activities, respectively, and chiral cyclic sulfamidate-fused imidazolidinones are speculated to have potential activities. However, the asymmetric synthesis of chiral cyclic sulfamidate-fused imidazolidinones is very limited thus far. In this paper, we have developed palladium-catalyzed [2 + 3] cycloaddition of benzo[e][1,2,3]oxathiazine 2,2-dioxides and 5-vinyloxazolidine-2,4-diones providing chiral cyclic sulfamidate-fused imidazolidinones containing a quaternary carbon stereocenter in high to excellent yields (70%-90%) with high diastereoselectivity (3:1 ∼ >20:1 dr) and excellent enantioselectivity (86%-98% enantiomeric excess (ee)) under the mild conditions, in which our newly developed adjustable phosphoramidite ligand at multiple sites played a key role in reactivity of the substrates and stereoselectivity of the products.