Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Peng Gao; Guanfeng Liang; Tong Ru; Xiaoyan Liu; Haifeng Qi; Aiqin Wang; Fen-Er Chen

doi:10.1038/s41467-021-25061-0

Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Nat Commun. 2021 Aug 4;12(1):4698. doi: 10.1038/s41467-021-25061-0.

Authors

Peng Gao^{1

2

3}, Guanfeng Liang^{4

5}, Tong Ru^{1

2}, Xiaoyan Liu⁶, Haifeng Qi⁶, Aiqin Wang⁶, Fen-Er Chen^{7

8

9}

Affiliations

¹ Engineering Center of Catalysis and Synthesis for Chiral Molecules, Department of Chemistry, Fudan University, Shanghai, China.
² Shanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Drugs, Shanghai, China.
³ College of Chemistry, Sichuan University, Chengdu, Sichuan, China.
⁴ Engineering Center of Catalysis and Synthesis for Chiral Molecules, Department of Chemistry, Fudan University, Shanghai, China. lianggfeng@fudan.edu.cn.
⁵ Shanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Drugs, Shanghai, China. lianggfeng@fudan.edu.cn.
⁶ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
⁷ Engineering Center of Catalysis and Synthesis for Chiral Molecules, Department of Chemistry, Fudan University, Shanghai, China. rfchen@fudan.edu.cn.
⁸ Shanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Drugs, Shanghai, China. rfchen@fudan.edu.cn.
⁹ College of Chemistry, Sichuan University, Chengdu, Sichuan, China. rfchen@fudan.edu.cn.

Abstract

Single-atom Rh catalysts present superior activity relative to homogeneous catalyst in olefins hydroformylation, yet with limited success in regioselectivity control. In the present work, we develop a phosphorus coordinated Rh₁ single-atom catalyst with nanodiamond as support. Benefiting from this unique structure, the catalyst exhibits excellent activity and regioselectivity in hydroformylation of arylethylenes with wide substrate generality, i.e., with high conversion (>99%) and high regioselectivity (>90%), which is comparable with the homogeneous counterparts. The coordination interaction between Rh₁ and surface phosphorus species is clarified by ³¹P solid-state NMR and X-ray absorption spectroscopy (XAS). Rh single atoms are firmly anchored over nanodiamond through Rh-P bonds, guaranteeing good stability in the hydroformation of styrene even after six runs. Finally, by using this catalyst, two kinds of pharmaceutical molecules, Ibuprofen and Fendiline, are synthesized efficiently with high yields, demonstrating a new prospect of single-atom catalyst in pharmaceutical synthesis.

Grants and funding

21902032/National Natural Science Foundation of China (National Science Foundation of China)