Asymmetric [3 + 2] Cycloaddition of Chiral <i>N</i>‑Phosphonyl Imines with Methyl Isocyanoacetate for Accessing 2‑Imidazolines with Switchable Stereoselectivity

Asymmetric [3 + 2] cycloaddition of chiral <i>N</i>-phosphonyl imines with methyl isocyanoacetate has been established, enabling controllable/switchable stereoselectivity access to 21 examples of cycloadducts with good to excellent chemical yields (up to 92%) and high diastereoselectivities (up to 99:1 dr). The cycloaddition reaction promoted by Cs₂CO₃ resulted in diastereoenriched (4<i>R</i>,5<i>S</i>)-products with >99:1 dr. However, it showed the reverse stereoselectivity as diastereoenriched (4<i>S</i>,5<i>R</i>) products when AgF was employed as the catalyst. The synthesis followed the group-assisted purification (GAP) chemistry/technology in which the pure 2-imidazoline products were readily provided by washing the crude products with cosolvents of hexane and ethyl acetate