C-C bond coupling with sp3 C-H bond via active intermediates from CO2 hydrogenation

Qianli Ma; Jianian Cheng; Xiaojing Wu; Jin Xie; Ruihui Zhang; Zhihe Mao; Hongfang Yang; Wenjun Fan; Jianrong Zeng; Johannes Hendrik Bitter; Guanna Li; Zelong Li; Can Li

doi:10.1038/s41467-024-55640-w

C-C bond coupling with sp³ C-H bond via active intermediates from CO₂ hydrogenation

Nat Commun. 2025 Jan 2;16(1):140. doi: 10.1038/s41467-024-55640-w.

Authors

Qianli Ma^#^{1

2}, Jianian Cheng^#^{1

2}, Xiaojing Wu^{1

2}, Jin Xie^{1

2}, Ruihui Zhang^{1

2}, Zhihe Mao^{1

2}, Hongfang Yang^{1

2}, Wenjun Fan³, Jianrong Zeng^{4

5}, Johannes Hendrik Bitter⁶, Guanna Li⁷, Zelong Li^{8

9

10}, Can Li^{11

12

13}

Affiliations

¹ Key Laboratory of advanced catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China.
² State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China.
³ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.
⁴ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, 201204, Shanghai, China.
⁵ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 201800, Shanghai, China.
⁶ Biobased chemistry and technology group, Wageningen University, Bornse Weilanden 9, 6708 WG, Wageningen, The Netherlands.
⁷ Biobased chemistry and technology group, Wageningen University, Bornse Weilanden 9, 6708 WG, Wageningen, The Netherlands. [email protected].
⁸ Key Laboratory of advanced catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China. [email protected].
⁹ State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China. [email protected].
¹⁰ State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, 730000, Lanzhou, China. [email protected].
¹¹ Key Laboratory of advanced catalysis, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China. [email protected].
¹² State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, China. [email protected].
¹³ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China. [email protected].

^# Contributed equally.

Abstract

Compared to the sluggish kinetics observed in methanol-mediated side-chain alkylation of methyl groups with sp³ C-H bonds, CO₂ hydrogenation emerges as a sustainable alternative strategy, yet it remains a challenge. Here, as far as we know, it is first reported that using CO₂ hydrogenation replacing methanol can conduct the side-chain alkylation of 4-methylpyridine (MEPY) over a binary metal oxide-zeolite Zn₄₀Zr₆₀O/CsX tandem catalyst (ZZO/CsX). This ZZO/CsX catalyst can achieve 19.6% MEPY single-pass conversion and 82% 4-ethylpyridine (ETPY) selectivity by using CO₂ hydrogenation, which is 6.5 times more active than methanol as an alkylation agent. The excellent catalytic performance is realized on the basis of the dual functions of the tandem catalyst: hydrogenation of CO₂ on the ZZO and activation of sp³ C-H bond and C-C bond coupling on the CsX zeolite. The thermodynamic and kinetic coupling between the tandem reactions enables the highly efficient CO₂ hydrogenation and C-C bond coupling. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations suggest that the CH_xO* (CH₂O*) species, rather than methanol produced from CO₂ hydrogenation, is the key intermediate to achieve the C-C bond coupling.