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Palladium-catalysed selective oxidative amination of olefins with Lewis basic amines

Nature Chemistry volume 14, pages 1118–1125 (2022)Cite this article

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Abstract

Amines are prominent in natural products, pharmaceutical agents and agrochemicals. Moreover, they are synthetically valuable building blocks for the construction of complex organic molecules and functional materials. However, amines, especially aliphatic and aromatic amines with free N–H bonds, tend to coordinate with transition metals and deactivate the catalyst, posing a tremendous challenge to applying Lewis basic amines in the amination of olefins. Here we present an example of oxidative amination of simple olefins with various Lewis basic amines. The combination of a palladium catalyst, 2,6-dimethyl-1,4-benzoquinone and a phosphorous ligand leads to the efficient synthesis of alkyl and aryl allylamines. A series of allylamines were obtained with good yields and excellent regio- and stereoselectivities. Intramolecular amination to synthesize tetrahydropyrrole and piperidine derivatives was also realized. Mechanistic investigations reveal that the reaction undergoes allylic C(sp3)–H activation and subsequent functionalization.

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Fig. 1: Catalytic oxidative amination of olefins for the synthesis of alkyl and aryl allylamines.
Fig. 2: Streamlining the synthesis of chemical drugs via palladium-catalysed oxidative amination.
Fig. 3: Mechanistic investigation of palladium-catalysed oxidative amination through control experiments.
Fig. 4: DFT study on the coordination competition between substrates and ligand and the operative catalytic cycle.

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Data availability

Crystallographic data for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2038362 (62). A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data are available in the main text or Supplementary Information.

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Acknowledgements

The authors thank the Ministry of Science and Technology of the People’s Republic of China (2016YFA0602900), the National Natural Science Foundation of China (21420102003) and the Key-Area Research and Development Program of Guangdong Province (2020B010188001) for financial support.

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Authors and Affiliations

  1. Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, P. R. China

    Yangbin Jin, Chunsheng Li, Meng Li, Wanqing Wu & Huanfeng Jiang

  2. School of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou, P. R. China

    Yaru Jing & Zhuofeng Ke

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Contributions

The project was conceived of and supervised by H.J. Y. Jin developed the palladium-catalysed selective oxidative amination of olefins with Lewis basic amines. C.L. contributed to expanding the scope for aromatic amines. M.L. and Y. Jin performed the reaction mechanism studies. Y. Jing and Z.K. performed DFT studies. W.W. wrote the manuscript and incorporated revisions suggested by all authors.

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Correspondence to Huanfeng Jiang.

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Nature Chemistry thanks the anonymous reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–18, Tables 1–10, experimental procedures, synthetic procedures, characterization data, DFT calculations and references.

Supplementary Data 1

Crystallographic data for compound 62; CCDC reference 2038362.

Supplementary Data 2

Crystallographic data for compound 62; CCDC reference 2038362.

Supplementary Data 3

Cartesian coordinates (x,y,z) for all optimized structures.

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Jin, Y., Jing, Y., Li, C. et al. Palladium-catalysed selective oxidative amination of olefins with Lewis basic amines. Nat. Chem. 14, 1118–1125 (2022). https://doi.org/10.1038/s41557-022-01023-x

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