image: Controllable Hydrogenation/Deuteration of Aryl Chlorides based on Photocatalytic Water-Splitting Strategy view more
Credit: ©Science China Press
Activation of inert C-Cl bonds has attracted significant interest due to the inherent fundamental challenge. Conventional dechlorination generally use flammable hydrogen gas (H2), metal hydrides, or organic donors (amines, alcohols, and Hantzsch ester) as hydrogenation reagents.
Despite high hydrogenation efficiency, these processes have significant drawbacks because of the risks involved while using a flammable gas at high pressure, or needing complex infrastructure to handle air and moisture-sensitive metal hydride reducing agents or expensive organic hydrogen donors. To this end, it is appealing to develop a sustainable process for the hydrogenation of chlorides using sustainable and readily available hydrogen-donors, whereas water is the most ideal candidate.
Recently, Chenliang Su's research group from Shenzhen University, China, proposed a photocatalytic water splitting technology to in-situ "bubble" H2 for controllable hydrogenation of aryl chlorides, whereas the water system is utilized as safe and sustainable H-donors instead of flammable H2.
Using isotopically labelled water (D2O), the strategy has been successfully applied to install deuterium at C-Cl of chlorides under mild conditions with high deuterium incorporation and good functional group tolerance for the first time, providing an attractive way for high incorporation of deuterium in drug molecules to improve their pharmacokinetic and toxicity profiles. "Pd nanosheets (Pd NSs) decorated crystallined polymeric carbon nitride (CPCN) are used as the bifunctional photocatalyst, whereas Pd NSs not only serve as cocatalyst of CPCN to generate and stabilize H (D)-species but also play a significant role in sequential activation and hydrogenation/deuteration of C-Cl bonds.", Prof. Su said.
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This research was funded by the National Natural Science Foundation of China (21972094, 51701127 and 21401190), China Postdoctoral Science Foundation (2017M612709), Guangdong Special Support Program, Pengcheng Scholar program, Shen-zhen Peacock Plan (KQJSCX20170727100802505 and KQTD2016053112042971), Educational Commission of Guangdong Province (2016KTSCX126), Foundation for Distinguished Young Talents in Higher Education of Guangdong (2018KQNCX221), Shenzhen Innova-tion Program (JCYJ 20170818142642395).
See the article:
Ling X, Xu YS, Wu, SP, Liu MF, Yang P, Qiu CT, Zhang GQ, Zhou HW, Su CL. A visible-light-photocatalytic water-splitting strategy for sustainable hydrogenation/deuteration of aryl chlorides. Sci. China Chem., 2020(386-392). DOI: 10.1007/s11426-019-9672-8.
https://link.springer.com/article/10.1007%2Fs11426-019-9672-8
http://engine.scichina.com/doi/10.1007/s11426-019-9672-8
Journal
Science China Chemistry