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Synthesis of monophosphines directly from white phosphorus

Nature Chemistry volume 13, pages 458–464 (2021)Cite this article

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Abstract

Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride.

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Fig. 1: Strategies for the transformation of P4 into monophosphorus products.
Fig. 2: Hydrostannylation of P4.
Fig. 3: Functionalization of phosphines (Bu3Sn)xPH3 − x and direct, ‘one-pot’ functionalization of P4.
Fig. 4: Further direct, ‘one-pot’ functionalization of P4.
Fig. 5: Recycling of the Bu3Sn moiety.
Fig. 6: Synthesis of THPC via in situ generation of Bu3SnH.
Fig. 7: Synthesis of THPC (17) via catalytic transformation of P4 into THP (16).

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information files.

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Acknowledgements

We thank O. Garcia Mancheño, K. Zeitler and J. J. Weigand for valuable discussions. Funding by the European Research Council (ERC CoG 772299) and the Alexander von Humboldt Foundation (postdoctoral fellowship for D.J.S.) is gratefully acknowledged.

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Authors and Affiliations

  1. Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany

    Daniel J. Scott, Jose Cammarata, Maximilian Schimpf & Robert Wolf

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Contributions

D.J.S. developed the hydrostannylation procedures, developed initial procedures for the formation of final products, and performed mechanistic studies. D.J.S. and J.C. optimized the synthesis, isolation and purification of products at increased scale, and the recovery and recycling of Bu3Sn-based by-products. D.J.S. and M.S. developed the catalytic synthesis of THPC. D.J.S. and R.W. conceived, oversaw and directed the project. D.J.S. prepared the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Daniel J. Scott or Robert Wolf.

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Competing interests

A patent covering all of the results described herein has been filed (as of 13 February 2020) by the University of Regensburg (EP 20,157,197.3; inventors, D.J.S. and R.W.). The authors declare no other competing interests.

Additional information

Peer review information Nature Chemistry thanks Jean-Paul Quintard, Willem Schipper and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 1H NMR spectrum for the photoreaction of P4 with 6 equiv. Bu3SnH.

The reaction was performed in PhMe and driven by 455 nm LED irradiation for 18 hours prior to acquisition, as described in the Methods section. Solvent resonances are marked with an asterisk and are truncated for clarity. The inset shows an expansion of the doublet resonance with 117/119Sn satellites attributed to the PH moiety of (Bu3Sn)2PH (3).

Extended Data Fig. 2 31P{1H} NMR spectrum for the photoreaction of P4 with 6 equiv. Bu3SnH.

The reaction was performed in PhMe and driven by 455 nm LED irradiation for 18 hours prior to acquisition, as described in the Methods section. The insets show expansions of the signals attributed to Bu3SnPH2 (2) and (Bu3Sn)2PH (3), and to (Bu3Sn)3P (4), highlighting the presence of 117/119Sn satellites.

Extended Data Fig. 3 31P NMR spectrum for the photoreaction of P4 with 6 equiv. Bu3SnH.

The reaction was performed in PhMe and driven by 455 nm LED irradiation for 18 hours. In this case, the reaction was performed in a sealed NMR tube fitted with a J. Young valve (see Supplementary Method 16), to avoid loss of PH3 (1) during manipulation. The insets show expansions of the signals attributed to PH3 (1), and to Bu3SnPH2 (2) and (Bu3Sn)2PH (3), highlighting their multiplicity due to 1J(31P-1H) couplings.

Extended Data Fig. 4 119Sn{1H} NMR spectrum for the photoreaction of P4 with 6 equiv. Bu3SnH.

The reaction was performed in PhMe and driven by 455 nm LED irradiation for 18 hours prior to acquisition, as described in the Methods section. The inset highlights the doublets attributed to Bu3SnPH2 (2), (Bu3Sn)2PH (3) and (Bu3Sn)3P (4).

Extended Data Fig. 5 31P{1H} NMR spectra for the photoreaction of P4 with 6 equiv. Bu3SnH in various solvents.

Reactions were otherwise identical to the example given in the Methods section and were driven by 455 nm LED irradiation for 20 hours.

Extended Data Fig. 6 Proposed balanced, overall equations for the formation of [Bn4P]Br (14).

a, In the absence of KHMDS, formation of PH3 as a stoichiometric byproduct is proposed to occur. b, In the presence of KHMDS, 14 is proposed to be the only stoichiometric phosphorus-containing product.

Extended Data Fig. 7 A proposed, outline mechanism for the catalytic transformation of P4 into THPC (17) via THP (16).

Hydrostannylation of P4 by Bu3SnH is followed by insertion of formaldehyde into P–Sn and P–H bonds. Solvolysis of the resulting Sn–O bonds releases THP, which is transformed into THPC upon eventual quenching with HCl. This step also releases Bu3SnOEt which can react with PMHS to regenerate Bu3SnH and thereby close the catalytic cycle.

Supplementary information

Supplementary Information

Characterization data, Supplementary Methods 1–42, Figs. 1–139 and Table 1.

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Scott, D.J., Cammarata, J., Schimpf, M. et al. Synthesis of monophosphines directly from white phosphorus. Nat. Chem. 13, 458–464 (2021). https://doi.org/10.1038/s41557-021-00657-7

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