Direct catalytic transformation of white phosphorus into arylphosphines and phosphonium salts

Abstract

Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P–C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving an initial oxidation of white phosphorus (P4) with hazardous chlorine gas and the subsequent displacement of chloride ions. Catalytic P4 organofunctionalization reactions have remained elusive, as they require multiple P–P bond-breaking and P–C bond-forming events to break down the P4 core, all of which must occur in a controlled manner. Herein, we describe an efficient transition-metal-catalysed process capable of forming P–C bonds from P4. Using blue-light photocatalysis, this method directly affords valuable triarylphosphines and tetraarylphosphonium salts in a single reaction step.

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Fig. 1: Functionalization of white phosphorus.
Fig. 2: Catalytic cycle.
Fig. 3: Time-resolved 31P{1H} NMR study.

Data availability

The data that support the figures within the paper and other findings of this study are available from the corresponding author on reasonable request.

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Acknowledgements

We thank K. Zeitler (Universität Leipzig), O. Garcia Mancheño (Universität Münster) and J. C. Slootweg (University of Amsterdam) for valuable comments on the manuscript, P. Nitschke (Gschwind group, University of Regensburg) for assistance with NMR measurements and B. Luy (Karlsruhe Institute of Technology) for providing the broadband pulse xyBEBOP. Support by the DFG graduate program ‘Chemical Photocatalysis’ (GRK 1626) and the European Research Council (ERC CoG 772299) is also gratefully acknowledged.

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Contributions

U.L. developed the initial catalytic procedure. U.L. and P.B.A. performed further optimization. U.L., P.B.A. and D.J.S. investigated the substrate scope. U.L. and D.J.S. performed mechanistic investigations. V.S. and R.M.G. performed in situ NMR studies. C.R. performed (spectro)electrochemical experiments. R.W. oversaw and directed the project. U.L. and D.J.S. prepared the manuscript, with input from all authors.

Corresponding author

Correspondence to Robert Wolf.

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Supplementary Information

Supplementary methods, discussion, Figures 1–62, Tables 1–6 and references

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Lennert, U., Arockiam, P.B., Streitferdt, V. et al. Direct catalytic transformation of white phosphorus into arylphosphines and phosphonium salts. Nat Catal 2, 1101–1106 (2019). https://doi.org/10.1038/s41929-019-0378-4

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