Catalyst-Free, Visible-Light-Driven Hydrogenation and Giese Addition of N-Hydroxyphthalimide Ester–Containing Polymers Using Hantzsch Esters
- 1School of Materials and Chemical Technology, Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Japan, 226-8501
- 2Japan Ground Self-Defense Force, Ichigaya Garrison, 5-1 Ichigaya Honmura-cho, Shinjuku-ku, Tokyo, Japan, 162-8802
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.
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BibTeX
@misc{eriguchi2026catalystfree,
title = {{Catalyst-Free, Visible-Light-Driven Hydrogenation and Giese Addition of N-Hydroxyphthalimide Ester–Containing Polymers Using Hantzsch Esters}},
author = {Yoichiro Eriguchi and Kosuke Sato and Shinsuke Inagi},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008271/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008271/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Catalyst-Free, Visible-Light-Driven Hydrogenation and Giese Addition of N-Hydroxyphthalimide Ester–Containing Polymers Using Hantzsch Esters
AU - Yoichiro Eriguchi
AU - Kosuke Sato
AU - Shinsuke Inagi
PY - 2026
DA - 2026/09/03
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008271/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008271/v1
AB - 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.
ER -