Metal-Free ROMP

Post-polymerization modification (PPM) via direct C-H functionalization is a powerful synthetic strategy to convert polymer feed-stocks into value-added products. We found that a metal-free, Se-catalyzed allylic C-H amination provided an efficient method for PPM of polynorbornenes (PNBs) produced via ring-opening metathesis polymerization. Inherent to the mechanism of the allylic amination, PPM on PNBs preserved the alkene functional groups along the polymer backbone, while also avoiding transposition of the double bonds. Amination using a series of aryl sulfonamides led to good control over the degree of functionalization, access to a range of functionalities, and tunable thermal properties from the resulting polymers.

Stereochemistry can have profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal-mediated ring-opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal-free ROMP. Ion-pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98%. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (-78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.

Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, and applications. This is often approached through the development of dynamic catalyst (or initiator) systems that use external stimuli to elicit discrete, site-specific transformations that impact the polymerization. Herein we highlight developments in polymerizations that are modulated by external stimuli, with particular focus on those systems that enable notable changes in kinetics, monomer selectivity, polymer architecture, or tacticity. Examples of external stimuli include chemical oxidants or reductants, light, applied voltage, and mechanical force.

Ring-opening metathesis polymerization (ROMP), which is derived from transition-metal-based olefin metathesis, has evolved into one of the most prevalent technologies for making functional polymeric materials in academia and in industry. The initial discovery of and advances in ROMP used ill-defined mixtures of metal salts to initiate polymerization. The initiators most commonly used today, developed with tremendous efforts, are well-defined metal−alkylidene complexes that have enabled a good mechanistic understanding of the polymerization as well as improvement of the initiators’ activity, stability, and functional group tolerance.

The evolution of ROMP has been decidedly metal-centric, with the path to accolades being paved primarily in ruthenium-, molybdenum-, and tungstenbased systems. Our departure from the ROMP trailhead was inspired in part by recent breakthroughs in radical-mediated polymerizations, whereby their mechanisms were leveraged to develop metal-free reaction conditions. Inventing a metal-free complement to traditional ROMP would essentially involve stepping away from decades of inorganic and organometallic developments, but with the promise of crossing new synthetic capabilities and curiosities. Driven by this motivation, as well as a community-inspired desire to develop “greener” controlled polymerizations, our team pioneered the search for, and discovery of, a wholly organic alternative to traditional metal-mediated ROMP. In this Account, we review our recent efforts to develop metal-free ring-opening metathesis polymerization (MF-ROMP), which is inspired by previous reports in electro- and photo-mediated organic transformations.

This work began with an exploration of the direct oxidation of enol ethers and the propensity of the ensuing radical cations to initiate ROMP. To overcome limitations of the electrochemical conditions, a photoredox-mediated method was investigated next, using photoexcited pyrylium salts to oxidize the enol ethers. With this system, we demonstrated the ability to produce ROMP products and temporally control the polymerization.

Further investigations into different aspects of the reaction included monomer scope, functional group tolerance, the impact of changing photocatalyst properties, and the ability to control molecular weight. The unique mechanism of MF-ROMP, along with the relative ease of synthesizing enol ether initiators, enabled the preparation of numerous polymeric materials that are hard to access through traditional metal-mediated pathways. At the end of this Account, we provide a perspective on future opportunities in this emerging area.