A rare earth hydride supported ruthenium catalyst for the hydrogenation of N-heterocycles: boosting the activity via a new hydrogen transfer path and controlling the stereoselectivity

Yong Wu; Hongen Yu; Yanru Guo; Xiaojing Jiang; Yue Qi; Bingxue Sun; Haiwen Li; Jie Zheng; Xingguo Li

doi:10.1039/c9sc04365a

A rare earth hydride supported ruthenium catalyst for the hydrogenation of N-heterocycles: boosting the activity via a new hydrogen transfer path and controlling the stereoselectivity

Chem Sci. 2019 Oct 11;10(45):10459-10465. doi: 10.1039/c9sc04365a. eCollection 2019 Dec 7.

Authors

Yong Wu¹, Hongen Yu¹, Yanru Guo¹, Xiaojing Jiang¹, Yue Qi¹, Bingxue Sun¹, Haiwen Li², Jie Zheng¹, Xingguo Li¹

Affiliations

¹ Beijing National Laboratory for Molecular Science (BNLMS) , College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China.
² Platform of Inter/Transdisciplinary Energy Research (Q-PIT) , International Research Center for Hydrogen Energy , International Institute for Carbon-Neutral Energy Research (I2CNER) , Kyushu University , 744 Motooka Nishi-ku , Fukuoka 819-0395 , Japan . Email: xgli@pku.edu.cn ; ; Tel: +86-10-62765930.

Abstract

Hydrogenation of N-heterocycles is of great significance for their wide range of applications such as building blocks in drug and agrochemical syntheses and liquid organic hydrogen carriers (LOHCs). Pursuing a better hydrogenation performance and stereoselectivity, we successfully developed a rare earth hydride supported ruthenium catalyst Ru/YH₃ for the hydrogenation of N-heterocycles, especially N-ethylcarbazole (NEC), the most promising LOHC. Full hydrogenation of NEC on Ru/YH₃ can be achieved at 363 K and 1 MPa hydrogen pressure, which is currently the lowest compared to previous reported catalysts. Furthermore, Ru/YH₃ shows the highest turnover number, namely the highest catalytic activity among the existing catalysts for hydrogenation of NEC. Most importantly, Ru/YH₃ shows remarkable stereoselectivity for all-cis products, which is very favorable for the subsequent dehydrogenation. The excellent performance of Ru/YH₃ originates from the new hydrogen transfer path from H₂ to NEC via YH₃. Ru/LaH₃ and Ru/GdH₃ also reveal good activity for hydrogenation of NEC and Ru/YH₃ also possesses good activity for hydrogenation of 2-methylindole, indicating that the use of rare earth hydride supported catalysts is a highly effective strategy for developing better hydrogenation catalysts for N-heterocycles.