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Palladium-catalysed enantioselective diacetoxylation of terminal alkenes

Nature Catalysis volume 4, pages 172–179 (2021)Cite this article

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Abstract

Optically pure 1,2-diols are one of the most privileged structural motifs. They are not only frequently found in natural products and drugs, but are also regarded as very useful synthons in organic synthesis. Asymmetric dioxygenation of alkenes could potentially provide a highly efficient and straightforward method for the synthesis of enantioenriched 1,2-diols. Although enantioselective dioxygenations on different alkenes have been studied widely, those on terminal alkenes remain elusive. Herein, we report a Pd(ii)-catalysed enantioselective diacetoxylation of terminal alkenes, including challenging substrates such as 1-propene and 1-butene. Notably, ligand engineering of the simple pyridinyl oxazoline ligand is essential for substantially increasing the catalytic reactivity of Pd(OAc)2. The method exhibits an exquisite selectivity for terminal alkenes, allowing precise asymmetric diacetoxylation reactions from feedstock alkenes to complex molecules bearing multiple alkenic moieties, which provides rapid and efficient access to various synthetically useful chiral 1,2-diols.

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Fig. 1: Catalytic AD of alkenes.
Fig. 2: The asymmetric diacetoxylation of alkenes using a palladium/Pyox catalyst.
Fig. 3: Scope of the asymmetric diacetoxylation of alkenes.
Fig. 4: Reaction of polyenes and synthetic applications of chiral 1,2-diacetates.
Fig. 5: Mechanistic investigation.

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Data availability

Source data are provided with this paper. Crystallographic data for the structures reported in this article are available from the Cambridge Crystallographic Data Centre with the following deposition numbers: CCDC 2024583 (22), CCDC 1998173 (Pd(L5)Cl2), CCDC 2024584 (Pd(L7)Cl2) and CCDC 2024585 (Pd(L1)Cl2). All other data supporting the findings of this study are available within the paper and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

Financial support was provided by the National Natural Science Foundation of China (grant numbers 21532009, 21971255, 21821002, 21790330 and 21761142010), the Science and Technology Commission of Shanghai Municipality (grant numbers 19590750400 and 17JC1401200), the Strategic Priority Research Program (number XDB20000000) and the Key Research Program of Frontier Sciences (QYZDJSSW-SLH055) of the Chinese Academy of Sciences. P.C. also thanks the Youth Innovation Promotion Association of the Chinese Academy of Sciences (number 2018292).

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Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry and Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China

    Bing Tian, Pinhong Chen, Xuebing Leng & Guosheng Liu

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Contributions

B.T. and G.L. conceived the work and designed the experiments. B.T. predominantly performed the laboratory experiments. X.L. collected and analysed the X-ray data. B.T., P.C. and G.L. analysed the data and wrote the manuscript.

Corresponding author

Correspondence to Guosheng Liu.

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The authors declare no competing interests.

Additional information

Peer review information Nature Catalysis thanks Erik Alexanian, Huanfeng Jiang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Tables 1–9, Figs. 1–9, methods, discussion and refs. 1–20.

Supplementary Data 1

X-ray structure of 22.

Supplementary Data 2

X-ray structure of Pd(L1)Cl2.

Supplementary Data 3

X-ray structure of Pd(L5)Cl2.

Supplementary Data 4

X-ray structure of Pd(L7)Cl2.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 5

Statistical source data.

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Tian, B., Chen, P., Leng, X. et al. Palladium-catalysed enantioselective diacetoxylation of terminal alkenes. Nat Catal 4, 172–179 (2021). https://doi.org/10.1038/s41929-021-00574-5

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