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Ni-catalysed dicarbofunctionalization for the synthesis of sequence-encoded cyclooctene monomers

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Abstract

The properties of polymeric materials can be modulated by factors such as sequence control or functional group modifications. However, the synthesis of new macromolecular scaffolds is limited by the accessibility of structurally diverse monomers. This work describes a one-step, nickel-catalysed synthesis of 5,6-diaryl cyclooctene monomers from the feedstock chemical 1,5-cyclooctadiene. The reaction proceeds in a modular, regio- and diastereoselective fashion, granting access to both homo- and hetero-diaryl cyclooctene monomers that smoothly undergo ring-opening metathesis polymerization (ROMP). The resulting 1,2-diaryl-substituted polymers possess sequences with head-to-head styrene dyads that have not been previously explored, giving rise to unique and tunable properties. Density functional theory calculations highlight mechanistic aspects of the nickel-catalysed diarylation reaction and the ruthenium-catalysed ROMP process, revealing a previously unappreciated role of the boronic ester in promoting migratory insertion, which was leveraged to provide enantioinduction.

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Fig. 1: Overview and concept.
Fig. 2: Reaction optimization and scope for the 5,6-diarylation of COD.
Fig. 3: Mechanistic studies of the Ni-catalysed diarylation of 1,5-cyclooctadiene.
Fig. 4: Ring-opening metathesis polymerization of diaryl cyclooctene.

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Data availability

The data that support the findings of this study are available within the paper and its Supplementary Information files. Experimental procedures, characterization data for all new compounds and details for DFT calculations can be found in the Supplementary Information. Crystallographic data for the structure reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2294340 (2i); 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 for the experimental work was provided by the Department of Energy (DE-SC0023205). The computational work was supported by the National Science Foundation (CHE-2102550). We thank the Schimmel Family Endowed Scholarship Fund for a Graduate Fellowship (C.Z.R.). We thank the Independent Research Fund Denmark (grant ID 10.46540/3102-00009B) for financial support (A.K.R.). Computational studies were performed at the Center for Research Computing at the University of Pittsburgh and the Advanced Cyberinfrastructure Coordination Ecosystem: Services & Support (ACCESS) program supported by NSF. We acknowledge Dr. M. Gembicky (UCSD) for X-ray crystallographic analysis.

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Author notes

  1. These authors contributed equally: Van T. Tran, Anne K. Ravn, Camille Z. Rubel, Mizhi Xu, Yue Fu.

Authors and Affiliations

  1. Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA

    Van T. Tran, Anne K. Ravn, Camille Z. Rubel & Keary M. Engle

  2. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA

    Mizhi Xu, Ethan M. Wagner & Will R. Gutekunst

  3. Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA

    Yue Fu & Peng Liu

  4. Chemical Process Development, Bristol Myers Squibb, New Brunswick, NJ, USA

    Steven R. Wisniewski

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Contributions

V.T.T., A.K.R. and C.Z.R. performed optimization and evaluated the scope of the nickel-catalysed 1,2-dicarbofunctionalization reaction. M.X. and E.M.W. carried out polymerization experiments. Y.F. and P.L. carried out computation work. S.R.W. performed kinetic experiments on the nickel-catalysed 1,2-dicarbofunctionalization reaction. V.T.T., P.L., W.R.G. and K.M.E. conceived the project. A.K.R., P.L., W.R.G. and K.M.E. wrote the manuscript with input from all authors.

Corresponding authors

Correspondence to Peng Liu, Will R. Gutekunst or Keary M. Engle.

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Nature Synthesis thanks Yifeng Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Thomas West, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Experimental procedures, characterization data for all new compounds and details for DFT calculations. Supplementary Figs. 1–132 and Tables 1–16.

Supplementary Data 1

Crystallographic data for 2i, CCDC 2294340.

Supplementary Data 2

Raw NMR spectroscopic data.

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Tran, V.T., Ravn, A.K., Rubel, C.Z. et al. Ni-catalysed dicarbofunctionalization for the synthesis of sequence-encoded cyclooctene monomers. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00618-1

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