Abstract
The reduction of epoxides has been recognized as an important method for the synthesis of alcohols using stoichiometric amounts of metal hydride reducing agents. However, homogeneous catalysis-enabled hydrogenation processes with molecular hydrogen remain scarce. Here, we present a general methodology for the synthesis of primary alcohols in high yields, selectively and under mild conditions, from aliphatic and aromatic epoxides. Crucial for the hydrogenation of terminal epoxides is the presence of an Fe(BF4)2.6H2O/tetraphos catalyst system. Compared to existing methods, which make use of noble metals, the presented protocol shows broad substrate scope and good functional group tolerance. The generality of this is showcased by transformation of various natural products, including steroids, terpenoids, sesquiterpenoids and drug derivatives, which give the desired alcohols in moderate to excellent yields. Mechanistic studies confirm the distinct feature of the catalyst system, which is active for Meinwald rearrangement of epoxides as well as for carbonyl hydrogenations.
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Data availability
CCDC 1895726 (S7), 1895727 (S9), 1895728 (S10), 1895729 (9a) and 1895730 (10′) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Further data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.
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Acknowledgements
The authors thank the analytic department (LIKAT) for their support, and the State of Mecklenburg-Western Pomerania, the Federal State of Germany (BMBF) and the EU (grant 670986) for financial support. The authors also thank W. Baumann (LIKAT) for helpful discussions regarding NMR analyses and D. Leonard (LIKAT) for assistance with manuscript preparation.
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M.B. and W. Liu. conceived and designed the experiments. W. Liu and W. Li performed the experiments and analysed the data. A.S. performed X-ray crystal structure analyses. K.J. participated in the discussions and supported the project. M.B. and W. Liu co-wrote the paper.
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Supplementary Information
Supplementary methods, Supplementary Tables 1-6, Supplementary references
compound S7
Crystallographic Data for compound S7
compound S9
Crystallographic Data for compound S9
compound S10
Crystallographic Data for compound S10
compound 9a
Crystallographic Data for compound 9a
compound 10’
Crystallographic Data for compound 10’
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Liu, W., Li, W., Spannenberg, A. et al. Iron-catalysed regioselective hydrogenation of terminal epoxides to alcohols under mild conditions. Nat Catal 2, 523–528 (2019). https://doi.org/10.1038/s41929-019-0286-7
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DOI: https://doi.org/10.1038/s41929-019-0286-7
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