Catalyst-Free, Visible-Light-Driven Hydrogenation and Giese Addition of N-Hydroxyphthalimide Ester–Containing Polymers Using Hantzsch Esters
Year: 2026
Type: preprint
Abstract: To address unfavorable monomer reactivity ratios and catalyst deactivation during olefin copolymerization with polar vinyl monomers, alternative synthesis methods, such as the postfunctionalization of N-hydroxyphthalimide (NHPI) ester–containing polymers, have attracted significant attention. Although conventional hydrogenation methods have successfully yielded olefin copolymers, they are limited due to their reliance on toxic, unstable reagents and significant scale-up challenges. Thus, we explored the visible-light-driven reaction of electron donor–acceptor (EDA) complexes between NHPI esters and safe, inexpensive Hantzsch esters. In this study, we established a catalyst-free, visible-light-driven hydrogenation strategy for NHPI estercontaining polymers via EDA-complex-mediated decarboxylation of side-chain groups. This methodology enabled the synthesis of diverse olefin copolymers, including acrylates, polyacrylonitrile, and polystyrene, and advanced gram-scale reactions under natural sunlight. Furthermore, we demonstrated that the undesired polymer crosslinking commonly observed in acrylonitrile copolymer reactions could be effectively suppressed by adjusting the light intensity. This strategy was applied to Giese addition, achieving a high degree of functionalization of up to 79%. Overall, this strategy represents a milestone toward green, sustainable polymer synthesis.
Source: ChemRxiv
Authors: Yoichiro Eriguchi, Kosuke Sato, Shinsuke Inagi
Institutions: Institute of Science Tokyo, Japan Ground Self-Defense Force
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G1889665402
OpenAlex ID: W7208753327