Sep 2026· Journal of the American Chemical Society· Vol 148 36, pp.
39348-39356
· 0 citations· 47 references
Medicine
Abstract
Radical homopolymerization of aliphatic alkynes remains a formidable challenge, primarily because the high reactivity of propagating vinyl radicals renders inevitable chain transfer via hydrogen atom transfer kinetically more favorable than chain propagation. By harnessing rationally designed distal sulfone-substituted aliphatic alkynes as monomers, here we report an efficient radical homopolymerization of aliphatic alkynes via 1,4-group transfer, affording a series of new polymers with defined ABC-type sequence. DFT calculations reveal that the 1,4-group transfer plays a critical role in facilitating chain propagation. The resulting polymers further exhibit outstanding performance as binders for high-temperature proton-exchange membrane fuel cells. Furthermore, the polymers can be chemically degraded to yield a diversity of valuable crotylamines. This work achieves the elusive radical polymerization of aliphatic alkynes that is inaccessible by traditional methods, providing a promising platform for the development of functional polymers.
Radical-mediated transition-metal-catalyzed C─H carbonylation represents a direct and powerful approach for the synthesis of carbonyl compounds; however, the stoichiometric oxidants typically required for hydrogen atom abstraction hamper the extensive application of these protocols and raise environmental concerns. In...
Cheng-Cheng Fan, Jia-Ning Wu, Peng Wang et al.· Angewandte Chemie· 0 citations
Acid-degradable vinyl polymers prepared by free-radical polymerization (FRP) remain rare despite their potential applications in photoresists, responsive materials, and drug delivery systems. Herein, a series of vinyl oxirane (VO) monomers were designed for radical ring-opening polymerization (rROP) to afford acid-degr...
Jia-Feng Chen, Hong-Gao Huang, Ning Wang et al.· Angewandte Chemie· 0 citations
Alkoxy radical-mediated hydroetherification offers an atom-economical approach for C-O bond construction. However, the difunctionalization of alkenes driven by alkoxy radicals remains elusive due to the inherent challenges associated with the generation and controlled reactivity of these reactive oxygen-centered radica...
Cyclobutene is a highly strained cyclic olefin that can undergo addition polymerization while retaining its four-membered ring as a cyclobutane unit in the polymer backbone. However, the strained structure and distinct reactivity of cyclobutene also make it susceptible to competing pathways, including ring opening an...
Meng Chen, Ming-Hang Ji, Sha-Na Tang· Polymer Science & Techno...· 0 citations
α‑Haloalkylboron compounds are valuable ambiphilic synthons, but the conventional ATRA reaction using vinyl‐Bpin often gives products that are unstable and difficult to isolate. In this study, we developed a copper‑catalyzed ATRA reaction using a sterically bulky protecting group, “OxB(oxazaborolidinone)”. OxB sterical...
Polyglycolide (PGA) is a leading biodegradable polyester, but controlled access to high-molecular-weight PGA remains challenging. Here, we introduce a covalent preorganization strategy that merges H-bond-mediated monomer activation and alkoxide-based chain propagation within a single molecular scaffold. Systematic vari...
