Lewis‐Acid‐Mediated Stereospecific Radical Polymerization of Acrylimides Bearing Chiral Oxazolidinones

Lewis acid (MgBr₂)‐catalyzed radical polymerization of acrylimides bearing chiral oxazolidinones gave highly isotactic polyacrylimides with up to >99 % meso tetrad (mmm) selectivity. Polymerization in the absence of Lewis acid gave atactic polymers with 80 % racemo diad (r) selectivity; the selectivity was deliberately tuned from 80 % r to >99 % mmm by varying the polymerization conditions. The polyacrylimide was quantitatively converted to corresponding polyacrylates while preserving the stereoregularity, thus providing a general method for the synthesis of atactic to isotactic polyacrylates.