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Mimicking hydrogen-atom-transfer-like reactivity in copper-catalysed olefin hydrofunctionalization

Nature Catalysis volume 7, pages 838–846 (2024)Cite this article

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Abstract

The renaissance of catalytic metal hydride hydrogen atom transfer (MHAT) offers advanced tools for radical chemistry on simple olefins. While 3d transition metals like cobalt, iron and manganese have been extensively studied in catalytic MHAT, the potential of copper remains unexplored. This is due to the polar reactivity exhibited by classical nucleophilic Cu(I)–H. Here we report copper-catalysed MHAT-like oxidative hydrofunctionalization reactions. In contrast to conventional Cu(I)–H chemistry, the putative Cu-MHAT process produces alkyl radicals with high chemoselectivity and regioselectivity, which are subsequently captured by Cu(II) species to undergo coupling reactions with a broad scope of oxygen-, nitrogen-, halogen- and carbon-based nucleophiles. Preliminary results suggest viable extension to asymmetric catalysis and radical polymerization. This work offers a complementary oxidative MHAT platform.

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Fig. 1: Alkene functionalization via Cu-MHAT: background and proposal.
Fig. 2: Selected optimizations, evaluation of alkenes and comparison with traditional metal hydrides.
Fig. 3: Scope for catalytic hydrofunctionalization via Cu-MHAT.
Fig. 4: Mechanistic studies.
Fig. 5: Mechanistic hypothesis, DFT calculations and further extensions.

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Data availability

The data that support the findings in this study are available within the Article and its Supplementary Information or available from the corresponding author upon request. Crystallographic data for the structure reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition number CCDC 2280327 (46). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

Financial support was provided by the Natural Science Foundation of China (22222101, 22350006 and 22171012), Beijing Natural Science Foundation (2242006) and Beijing National Laboratory of Molecular Sciences (BNLMS). Computation was supported by the high-performance computing platform of Peking University (PKU). We thank X. Zhang (PKU) and H. Fu (PKU) for assistance with NMR spectroscopy and Y. Qiu (PKU) for assistance with X-ray crystallography. H.H. and J.W. acknowledge the PKU President’s Fellowship for Undergraduate Research.

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Authors and Affiliations

  1. Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Jun-Jie Wang, He Huang, Han-Li Sun, Fan Yang, Jun Wen & Rong Zhu

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  1. Jun-Jie Wang
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  2. He Huang
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  3. Han-Li Sun
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Contributions

R.Z. proposed the transformation. J.-J.W., H.H., H.-L.S., F.Y. and J.W. conducted the experimental investigation. R.Z. and J.-J.W. wrote the manuscript. R.Z. directed the research.

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Correspondence to Rong Zhu.

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Nature Catalysis thanks Shuanglin Qu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Data 1

The .cif file for compound 46.

Supplementary Data 2

The .hkl file for compound 46.

Supplementary Data 3

The checkCIF file for compound 46.

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Wang, JJ., Huang, H., Sun, HL. et al. Mimicking hydrogen-atom-transfer-like reactivity in copper-catalysed olefin hydrofunctionalization. Nat Catal 7, 838–846 (2024). https://doi.org/10.1038/s41929-024-01182-9

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