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Low-valent tungsten redox catalysis enables controlled isomerization and carbonylative functionalization of alkenes

Nature Chemistry volume 14, pages 632–639 (2022)Cite this article

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Abstract

The controlled isomerization and functionalization of alkenes is a cornerstone achievement in organometallic catalysis that is now widely used throughout industry. In particular, the addition of CO and H2 to an alkene, also known as the oxo-process, is used in the production of linear aldehydes from crude alkene feedstocks. In these catalytic reactions, isomerization is governed by thermodynamics, giving rise to functionalization at the most stable alkylmetal species. Despite the ubiquitous industrial applications of tandem alkene isomerization/functionalization reactions, selective functionalization at internal positions has remained largely unexplored. Here we report that the simple W(0) precatalyst W(CO)6 catalyses the isomerization of alkenes to unactivated internal positions and subsequent hydrocarbonylation with CO. The six- to seven-coordinate geometry changes that are characteristic of the W(0)/W(II) redox cycle and the conformationally flexible directing group are key factors in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for in situ functionalization.

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Fig. 1: Overview of tungsten reactivity and isomerization–carbonylation reactions.
Fig. 2: The synthesis and reactivity of model W(II) intermediates was evaluated.
Fig. 3: Mechanistic experiments and deuterium-labelling studies.
Fig. 4: Computed reaction energy profile of the isomerization–carbonylation of 1a.

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Data availability

All data generated or analysed during this study are included in this article (and its Supplementary Information). The structures of W-2, W-3, W-3′, W-4 and 2u in the solid state were determined by single-crystal X-ray diffraction and the crystallographic data have been deposited with the Cambridge Crystallographic Data Centre: CCDC 2020047 (W-2), 2050458 (W-3), 2045639 (W-3′), 2110274 (W-4), 2008992 (2u). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

B. Sanchez and E. Sturgell (Scripps Research Automated Synthesis Facility) are acknowledged for HPLC and chiral SFC analysis. H. Nguyen, K. McClymont, T. Huffman and C. Bi are acknowledged for donation of various starting materials. We also thank J. Vantourout, C. Landis, J. Figueroa and H. Renata for helpful discussions. Financial support for this work was provided by the National Institutes of Health R35GM125052 (K.M.E.), R35GM128779 (P.L) and 1S10OD025208 (J.S.C.). We acknowledge USTC for sponsoring Z.-Y.Q. with a summer exchange scholarship. DFT calculations were performed at the Center for Research Computing at the University of Pittsburgh, the Frontera supercomputer at the Texas Advanced Computing Center, and the Extreme Science and Engineering Discovery Environment (XSEDE) supported by the NSF.

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Authors and Affiliations

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

    Tanner C. Jankins, Zi-Yang Qin & Keary M. Engle

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

    William C. Bell, Yu Zhang & Peng Liu

  3. Automated Synthesis Facility, The Scripps Research Institute, La Jolla, CA, USA

    Jason S. Chen

  4. Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, USA

    Milan Gembicky

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  1. Tanner C. Jankins
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Contributions

T.C.J. carried out all the experiments and data analysis. Z.-Y.Q. carried out synthesis of various alkene starting materials. J.S.C. helped design and perform pressurized experiments. M.G. carried out collection and analysis of X-ray data. W.C.B, Y.Z. and P.L. carried out computation work. T.C.J., P.L. and K.M.E. wrote the manuscript with input from all authors.

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Correspondence to Peng Liu or Keary M. Engle.

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Nature Chemistry thanks Graham Dobereiner and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Data regarding reaction optimization, synthetic and experimental procedures, full characterization data including NMR spectra X-ray crystallographic data, 26 supplementary figures, and 38 supplementary tables.

Supplementary Data 1

xyz coordinates for DFT calculations.

Supplementary Data 2

Original NMR data in MNova format.

Supplementary Data 3

Crystallographic data for compound W-2; CCDC reference 2020047.

Supplementary Data 4

Crystallographic data for compound W-3; CCDC reference 2050458.

Supplementary Data 5

Crystallographic data for compound W-3’; CCDC reference 2045639.

Supplementary Data 6

Crystallographic data for compound W-4; CCDC reference 2110274.

Supplementary Data 7

Crystallographic data for compound 2u; CCDC 2008992.

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Jankins, T.C., Bell, W.C., Zhang, Y. et al. Low-valent tungsten redox catalysis enables controlled isomerization and carbonylative functionalization of alkenes. Nat. Chem. 14, 632–639 (2022). https://doi.org/10.1038/s41557-022-00951-y

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