Metal-Free Stereoselective Cationic Polymerization of Vinyl Ethers by Employing a Confined Brønsted Acid as the Catalyst

The properties of poly(vinyl ether)s (PVEs) are highly dependent on their tacticity, and the appealing thermoplastics features of isotactic PVEs have drawn considerable efforts to develop stereoselective cationic polymerization methods to access this class of polymers. However, re-ported methods that could achieve a high degree of tacticity control are limited to process employing metal-based Lewis acids, and with various limitations on catalyst loading, monomer scope, etc. Here, we introduce a metal-free stereoselective cationic polymerization of vinyl ethers by employing a class of chiral confined Brønsted acids, imidodiphos-phorimidates (IDPis), as the catalyst. This organocatalytic approach features its metal free conditions, high efficiency, high stereoselectivity, single catalyst system, operation simplicity, etc.