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Redox-neutral conversion of ubiquitous PV sources to a versatile PO2+ phosphorylation reagent

Nature Synthesis volume 2, pages 972–979 (2023)Cite this article

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Abstract

Phosphorus and its compounds are a cornerstone of biological life, as well as finding applications in material science, for example, as flame retardants, battery electrolytes or catalysts. In most applications, phosphorus-containing fine chemicals are in the naturally occurring and most stable oxidation state +V of the element; however, syntheses to these compounds from primary PV sources rely on an energy-consuming and wasteful redox detour via elemental white phosphorus (P4) and its subsequent (oxy)chlorination to PCl3, PCl5 and POCl3. Here we report an approach using trifluoromethanesulfonic anhydride (Tf2O) and pyridine to directly cleave P–O bonds in ubiquitous PV sources to form the versatile PO2+ phosphorylation agent (pyridine)2PO2[OTf] (1[OTf]), whose preparation and mechanism of formation is discussed. Harnessing its reactivity towards various nucleophiles such as amines, alcohols and pseudohalogenides, 1[OTf] then provides redox-neutral access to a range of value-added PV chemicals downstream of low-cost phosphoric acid or other phosphate sources.

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Fig. 1: Comparison of different routes to commercial phosphorus compounds by their oxidation state.
Fig. 2: Reaction mechanism for the onio-ligand-assisted deoxygenation of various phosphate sources using triflic anhydride and pyridine.
Fig. 3: Synthesis of 1[OTf] from different PV sources and subsequent functionalization with N-, O- and C-nucleophiles.
Fig. 4: Synthesis of 1[OTf] from organophosphate esters such as OP(OMe)3 (TMP), OP(OEt)3 (TEP), OP(OnBu)3 (TBP) and D2EHPA.

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Data availability

All data needed to evaluate the conclusions of this work are present in the manuscript and/or in Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2232178 (1[OTf]), 2232179 (4), 2232180 (5a[OTf]), 2232181 (5b[OTf]), 2232182 (6[OTf]), 2232183 ([Na]8a), 2232184 ([Na]8b), 2232185 ([Na]8c), 2232186 (9), 2232187 (15), 2232188 (17a) and 2250333 (17b). Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.

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The code is not available.

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Acknowledgements

We thank the European Research Council (ERC starting grant, SynPhos-307616), the German Science foundation (WE 4621/6-1) and TU Dresden for financial support. T.S. thanks the Studienstiftung des Deutschen Volkes for a doctoral fellowship. R. Schoemaker and S. Schulz are gratefully acknowledged for their help and discussion regarding this project. We thank P. Lange for experimental assistance and elemental analysis (EA) measurements and U. Schwarzenbolz for high resolution mass spectrometry (HRMS) measurements. Solvay Chemicals is gratefully acknowledged for their donation of the chemicals Me3SiOTf and Tf2O.

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Author notes

  1. These authors contributed equally: Tobias Schneider, Kai Schwedtmann.

Authors and Affiliations

  1. Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Tobias Schneider, Kai Schwedtmann, Jannis Fidelius & Jan J. Weigand

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Contributions

T.S., K.S. and J.J.W. conceptualized the deoxygenation procedure, optimized the reaction conditions and performed mechanistic studies. T.S. and K.S. optimized the synthesis, isolation and purification of products from the phosphorylation reagent. J.F. and J.J.W. were responsible for collecting X-ray data and refinement. K.S. and J.J.W. conceived, oversaw and directed the project. J.J.W. was responsible for funding acquisition. T.S., K.S. and J.J.W. prepared the initial draft of the paper. All authors discussed the results and commented on the paper.

Corresponding author

Correspondence to Jan J. Weigand.

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Competing interests

Two patent applications covering the content of this work have been submitted by the TU Dresden (EP 21209296.9 and DE 102022120599.1). The authors declare that they have no other competing interests.

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Extended data

Extended Data Fig. 1 Molecular structures of (a) 1+ in 1[OTf] ⋅ 0.5 Py and (b) 4.

Thermal ellipsoids are displayed at 50 % probability level. Hydrogen atoms, solvent molecules and triflate anions are omitted for clarity.

Extended Data Fig. 2 31P NMR spectra (pyridine-d5, 320 K) of the reaction solution of H3PO4 with 2.2 eq. of TfPy[OTf] after varying reaction times.

The ongoing deoxygenation of intermediate 4 (δ(31P) = –17.5 ppm) to phosphinate 1+ (δ(31P) = –15.2 ppm) is observed.

Extended Data Fig. 3 31P{1H} NMR spectra (CH3NO2, C6D6-capillary, 300 K) of the reaction of H3PO4 with different amounts of TfPy[OTf] (1.00 eq., 1.25 eq., 1.50 eq., 1.75 eq.).

Several intermediates were identified by their characteristic signal patterns known to the literature37. PO43−: δ(31P) = 2.4 ppm (s); P2O74−: δ(31P) = – 8.4 ppm (s); P3O93−: δ(31P) = – 20.0 ppm (s); P4O124−: δ(31P) = –21.8 ppm (s); P4O112−: A2X2-spinsystem, δ(A) = – 36.9 ppm (t), δ(X) = – 26.3 ppm (t), 2JPP = 25.5 Hz; P4O136−: AX3-spinsystem, δ(A) = – 33.3 ppm (q), δ(X) = – 23.0 ppm (d), 2JPP = 21.9 Hz; 32−: AX-spinsystem, δ(A) = – 19.3 ppm (d), δ(X) = – 16.8 ppm (d), 2JPP = 18.2 Hz; 4: δ(31P) = – 17.3 ppm (s). Signals of higher, asymmetrically condensed phosphates which could not be assigned a structure are marked with asterisks (*).

Extended Data Fig. 4 Molecular structures of (a) 5a+ in 5a[OTf] ⋅ CH2Cl2; (b) 5b+ in 5b[OTf] and (c) 6+ in 6[OTf].

Thermal ellipsoids are displayed at 50 % probability level. Hydrogen atoms, solvent molecules and triflate anions are omitted for clarity.

Extended Data Fig. 5 (a) Section of the network structure of 17a ⋅ NaOTf ⋅ CH3CN and (b) molecular structure of 17b in 17b ⋅ CH3CN.

Thermal ellipsoids are displayed at 50 % probability level. Hydrogen atoms and non-coordinating solvent molecules are omitted for clarity.

Supplementary information

Supplementary Information

Supplementary materials and methods, text, Figs. 1–146, Tables 1–4 and References 1–19.

Supplementary Data 1

Crystal data of 1, CCDC 2232178.

Supplementary Data 2

Crystal data of 4, CCDC 2232179.

Supplementary Data 3

Crystal data of 5a, CCDC 2232180.

Supplementary Data 4

Crystal data of 5b, CCDC 2232181.

Supplementary Data 5

Crystal data of 6, CCDC 2232182.

Supplementary Data 6

Crystal data of 8a, CCDC 2232183.

Supplementary Data 7

Crystal data of 8b, CCDC 2232184.

Supplementary Data 8

Crystal data of 8c, CCDC 2232185.

Supplementary Data 9

Crystal data of 9, CCDC 2232186.

Supplementary Data 10

Crystal data of 15, CCDC 2232187.

Supplementary Data 11

Crystal data of 17a, CCDC 2232188.

Supplementary Data 12

Crystal data of 17b, CCDC 2250333.

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Schneider, T., Schwedtmann, K., Fidelius, J. et al. Redox-neutral conversion of ubiquitous PV sources to a versatile PO2+ phosphorylation reagent. Nat. Synth 2, 972–979 (2023). https://doi.org/10.1038/s44160-023-00344-0

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