Synthesis of piperidines and pyridine from furfural over a surface single-atom alloy Ru1CoNP catalyst

Haifeng Qi; Yurou Li; Zhitong Zhou; Yueqiang Cao; Fei Liu; Weixiang Guan; Leilei Zhang; Xiaoyan Liu; Lin Li; Yang Su; Kathrin Junge; Xuezhi Duan; Matthias Beller; Aiqin Wang; Tao Zhang

doi:10.1038/s41467-023-42043-6

Synthesis of piperidines and pyridine from furfural over a surface single-atom alloy Ru₁Co_NP catalyst

Nat Commun. 2023 Oct 10;14(1):6329. doi: 10.1038/s41467-023-42043-6.

Authors

Haifeng Qi^#^{1

2}, Yurou Li^#³, Zhitong Zhou¹, Yueqiang Cao³, Fei Liu¹, Weixiang Guan¹, Leilei Zhang¹, Xiaoyan Liu¹, Lin Li¹, Yang Su¹, Kathrin Junge², Xuezhi Duan⁴, Matthias Beller⁵, Aiqin Wang^{6

7}, Tao Zhang^{1

8}

Affiliations

¹ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
² Leibniz-Institut für Katalyse, Albert-Einstein-Straße 29a, Rostock, 18059, Germany.
³ State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China.
⁴ State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China. xzduan@ecust.edu.cn.
⁵ Leibniz-Institut für Katalyse, Albert-Einstein-Straße 29a, Rostock, 18059, Germany. matthias.beller@catalysis.de.
⁶ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. aqwang@dicp.ac.cn.
⁷ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. aqwang@dicp.ac.cn.
⁸ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.

^# Contributed equally.

Abstract

The sustainable production of value-added N-heterocycles from available biomass allows to reduce the reliance on fossil resources and creates possibilities for economically and ecologically improved synthesis of fine and bulk chemicals. Herein, we present a unique Ru₁Co_NP/HAP surface single-atom alloy (SSAA) catalyst, which enables a new type of transformation from the bio-based platform chemical furfural to give N-heterocyclic piperidine. In the presence of NH₃ and H₂, the desired product is formed under mild conditions with a yield up to 93%. Kinetic studies show that the formation of piperidine proceeds via a series of reaction steps. Initially, in this cascade process, furfural amination to furfurylamine takes place, followed by hydrogenation to tetrahydrofurfurylamine (THFAM) and then ring rearrangement to piperidine. DFT calculations suggest that the Ru₁Co_NP SSAA structure facilitates the direct ring opening of THFAM resulting in 5-amino-1-pentanol which is quickly converted to piperidine. The value of the presented catalytic strategy is highlighted by the synthesis of an actual drug, alkylated piperidines, and pyridine.