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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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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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.
The authors declare no competing interests.
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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.
xyz coordinates for DFT calculations.
Original NMR data in MNova format.
Crystallographic data for compound W-2; CCDC reference 2020047.
Crystallographic data for compound W-3; CCDC reference 2050458.
Crystallographic data for compound W-3’; CCDC reference 2045639.
Crystallographic data for compound W-4; CCDC reference 2110274.
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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