The control of the tacticity of synthetic polymers enables the realization of emergent physical properties from readily available starting materials. While stereodefined polymers derived from nonpolar vinyl monomers can be efficiently prepared using early transition metal catalysts, general methods for the stereoselective polymerization of polar vinyl monomers remain underdeveloped. We recently demonstrated asymmetric ion pairing catalysis as an effective approach to achieve stereoselective cationic polymerization of vinyl ethers. Herein, we provide a deeper understanding of stereoselective ion-pairing polymerization through comprehensive experimental and computational studies. These findings demonstrate the importance of ligand deceleration effects for the identification of reaction conditions that enhance stereoselectivity, which was supported by computational studies that identified the solution-state catalyst structure. An evaluation of monomer substrates with systematic variations in steric parameters and functional group identities established key structure−reactivity relationships for stereoselective homo-and copolymerization. Expansion of the monomer scope to include enantioenriched vinyl ethers enabled the preparation of an isotactic poly(vinyl ether) with the highest stereoselectivity (95.1% ± 0.1 meso diads) reported to date, which occurred when monomer and catalyst stereochemistry were fully matched under a triple diastereocontrol model. The more complete understanding of stereoselective cationic polymerization reported herein offers a foundation for the design of improved catalytic systems and for the translation of isotactic poly(vinyl ether)s to applied areas.

Isotactic poly(vinyl ether)s (PVEs) have recently been identified as a new class of semicrystalline thermoplastics with a valuable combination of mechanical and interfacial properties. Currently, methods to synthesize isotactic PVEs are limited to strong Lewis acids that require a high catalyst loading and limit the accessible scope of monomer substrates for polymerization. Here, we demonstrate the first Brønsted acid catalyzed stereoselective polymerization of vinyl ethers. A single-component imidodiphosphorimidate catalyst exhibits a sufficiently low pK a to initiate vinyl ether polymerization and acts as a chiral conjugate base to direct the stereochemistry of monomer addition to the oxocarbenium ion reactive chain end. This Brønsted acid catalyzed stereoselective polymerization enabled an expanded substrate scope compared to previous methods, the use of chain transfer agents to lower catalyst loading, and the capability to recycle the catalyst for multiple polymerizations.

A series of isotactic, semicrystalline vinyl ether copolymers (up to 94% meso diads) were synthesized using a chiral BINOL-based phosphoric acid in combination with a titanium Lewis acid. This stereoselective cationic polymerization enabled the systematic tuning of both glass transition (T g ) and melting temperature (T m ) in copolymers derived from alkyl vinyl ethers (i.e., ethyl, butyl, isobutyl). Additionally, a vinyl ether comonomer bearing an acylprotected alcohol was utilized as a platform for postfunctionalization.Copolymers containing the masked alcohols were shown to undergo deprotection and subsequent coupling with a desired acid chloride. Collectively, these results highlight the diverse material properties and expanded chemical space accessible through stereoselective cationic polymerization mediated by a chiral anion.

A series of isotactic, semicrystalline vinyl ether copolymers (up to 94% <i>meso</i> diads) were synthesized using a chiral BINOL-based phosphoric acid in combination with a titanium Lewis acid. This stereoselective cationic polymerization enabled the systematic tuning of both glass-transition (<i>T</i>_g) and melting temperature (<i>T</i>_m) in copolymers derived from alkyl vinyl ethers (<i>i.e.</i>, ethyl, butyl, isobutyl). Additionally, a vinyl ether comonomer bearing an acyl-protected alcohol was utilized as a platform for post-functionalization. Copolymers containing the masked alcohols were shown to undergo facile deprotection and subsequent coupling with a desired acid chloride. Collectively, these results highlight the diverse material properties and expanded chemical space accessible through stereoselective cationic polymerization mediated by a chiral anion.

A series of isotactic, semicrystalline vinyl ether copolymers (up to 94% <i>meso</i> diads) were synthesized using a chiral BINOL-based phosphoric acid in combination with a titanium Lewis acid. This stereoselective cationic polymerization enabled the systematic tuning of both glass-transition (<i>T</i>_g) and melting temperature (<i>T</i>_m) in copolymers derived from alkyl vinyl ethers (<i>i.e.</i>, ethyl, butyl, isobutyl). Additionally, a vinyl ether comonomer bearing an acyl-protected alcohol was utilized as a platform for post-functionalization. Copolymers containing the masked alcohols were shown to undergo facile deprotection and subsequent coupling with a desired acid chloride. Collectively, these results highlight the diverse material properties and expanded chemical space accessible through stereoselective cationic polymerization mediated by a chiral anion.