Asymmetric cycloaddition reactions between 2-benzopyrylium-4-olates and 3-(2-alkenoyl)-2-oxazolidinones in the presence of 2,6-bis(oxazolinyl)pyridine-lanthanoid complexes

Highly enantioselective (96% ee) and endo-selective (>99:1) cycloaddition reactions were observed between carbonyl ylides, generated from o-(p-bromobenzyloxy)carbonyl-α-diazoacetophenone, and 3-crotonoyl-2-oxazolidinone using (4S,5S)-Pybox-4,5-Ph₂-Yb(OTf)₃ (20 mol %) as the chiral Lewis acid catalyst. In contrast, high exo-selectivity (exo/endo=82:18; 96% ee, exo) was observed for the reaction of o-methoxycarbonyl-α-diazoacetophenone with 3-acryloyl-2-oxazolidinone under similar conditions as reported previously. In the case of cycloaddition reactions between 2-benzopyrylium-4-olate, generated from o-methoxycarbonyl-α-diazoacetophenone, and 3-cinnamoyl- or 3-[(E)-3-(ethoxycarbonyl)propenoyl]-2-oxazolidinones, using the same chiral Lewis acid, the reaction favored the endo-adduct with relatively good enantioselectivity (72 and 78% ee, respectively).