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Nickel-catalysed regio- and stereoselective acylzincation of unsaturated hydrocarbons with organozincs and CO

Nature Synthesis volume 2, pages 261–274 (2023)Cite this article

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Abstract

Carbometallation of unsaturated hydrocarbons is one of the most straightforward functionalizations of carbon–carbon unsaturated bonds; however, the analogous acylmetallation remains a significant synthetic challenge. Here, we disclose the nickel-catalysed acylzincation of ynamides, oxabicyclic alkenes and α,β-unsaturated ketones with organozinc reagents under 1 atm of CO, featuring excellent functional group tolerance, a broad substrate scope and mild conditions. The acyl functionality generated in situ from an organozinc reagent can be viewed as a nucleophilic synthon, and the corresponding acylzincation intermediate is trapped via intermolecular reaction with electrophiles. Alternatively, the intermediate can undergo an intramolecular Truce–Smiles rearrangement or aldol condensation to afford tetrasubstituted enones, multisubstituted benzocyclohexane derivatives and cyclopentenones. This method is applied to the formal synthesis of the anthracyclinone antibiotic daunomycinone, as well as to prepare functionalized 1,3-dienones possessing aggregation-induced emission activity. The syn metallation of acyl nickel intermediates with unsaturated hydrocarbons allows for the complete regioselective and highly stereoselective formation of functionalized zinc intermediates. Furthermore, density functional theory calculations show that acylmetallation is lower in energy than alkylmetallation, and demonstrates that favourable interaction energies lead to a lower energy transition state for formation of the major regioisomer.

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Fig. 1: Transition metal-catalysed carbometallation and acylmetallation of unsaturated C–C bonds.
Fig. 2: Synthetic applications.
Fig. 3: Mechanism studies.

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Data availability

The crystallographic data for compound 5af are available from the Cambridge Crystallographic Data Centre under deposition number CCDC 2054942 (https://www.ccdc.cam.ac.uk/structures). All other data to support the conclusions are available in the main text or the Supplementary Information.

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Acknowledgements

This work was supported by NSFC/China (grant nos. 21702060 and 22171079), the National Science Foundation (grant no. CHE-1764328), Natural Science Foundation of Shanghai (grant no. 21ZR1480400), Shanghai Rising-Star Program (grant no. 20QA1402300), Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (grant no. B16017), the Fundamental Research Funds for the Central Universities and the China Postdoctoral Science Foundation (grant no. 2021M701197). A.T. acknowledges the support of the National Institutes of Health under Ruth L. Kirschstein National Research Service Award F32GM134709. Calculations were performed on the Hoffman2 cluster at the University of California, Los Angeles, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (grant no. OCI-1053575). We thank the Analysis and Testing Center of East China University of Science and Technology for help with NMR spectroscopy analysis.

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  1. These authors contributed equally: Yangyang Weng, Yetong Zhang, Aneta Turlik, Xianqing Wu.

Authors and Affiliations

  1. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, China

    Yangyang Weng, Yetong Zhang, Xianqing Wu, Haiyan Li, Fan Fei, Yongkang Yao, Chenglong Wang, Zhiqian Guo, Jingping Qu & Yifeng Chen

  2. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Aneta Turlik & K. N. Houk

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Contributions

Y.W. and Y.C. conceived the project. Y.W., Y.Z., X.W., H.L., F.F. and C.W. performed the experiments under the supervision of J.Q. and Y.C. A.T. performed DFT calculations under the supervision of K.N.H. Y.Y. performed the photophysical properties tests under the supervision of Z.G. Y.W., X.W., A.T., K.N.H. and Y.C. wrote the manuscript with feedback from all authors.

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Correspondence to K. N. Houk or Yifeng Chen.

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Nature Synthesis thanks Long-Wu Ye and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary Information

Experimental details, Supplementary Fig. 1 and Tables 1–4.

Supplementary Data 1

Crystallographic data for compound 5af, CCDC 2054942.

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Weng, Y., Zhang, Y., Turlik, A. et al. Nickel-catalysed regio- and stereoselective acylzincation of unsaturated hydrocarbons with organozincs and CO. Nat. Synth 2, 261–274 (2023). https://doi.org/10.1038/s44160-022-00208-z

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