Closed-loop hydrostannylation of white phosphorus using Bu3SnCl and NaBH4: one-pot access to organophosphorus compounds

Michael Mende; Lina Heidkamp; Robert Wolf; Daniel J. Scott

doi:10.1039/d6dt01334a

Closed-loop hydrostannylation of white phosphorus using Bu₃SnCl and NaBH₄: one-pot access to organophosphorus compounds

Michael Mende
, Lina Heidkamp
, Robert Wolf
, Daniel J. Scott

University of Regensburg

Research output: Contribution to journal › Article › peer-review

Abstract

The direct functionalization of white phosphorus (P₄) is gaining attention as an alternative to state-of-the-art multi-step processes. The hydrostannylation of P₄ affords valuable monophosphorus compounds directly via a hydrostannylphosphine mixture (Bu₃Sn)_xPH_3−x (where x = 0–3) that reacts with suitable electrophiles. However, previous reports required terminal reductants which are infeasible for industrial-scale applications. Here, we report an improvement in this chemistry using NaBH₄ as the terminal reducing agent, generating the key hydrostannylation agent Bu₃SnH in situ from Bu₃SnCl. The resulting (Bu₃Sn)_xPH_3−x mixtures were successfully functionalized towards useful P₁ compounds. Furthermore, we present the ‘one-pot’ preparation of tetrakis(hydroxymethyl)phosphonium chloride (THPC), the subsequent direct recycling of Bu₃SnCl, and preliminary attempts towards the catalytic synthesis of THPC.

Original language	English
Number of pages	5
Journal	Dalton Transactions
Early online date	17 Jun 2026
DOIs	https://doi.org/10.1039/d6dt01334a
Publication status	E-pub ahead of print - 17 Jun 2026

Data Availability Statement

The data supporting this article have been included as part of
the supplementary information (SI). Supplementary information
is available. See DOI: https://doi.org/10.1039/d6dt01334a

Acknowledgements

Financial support by the DFG (RW, WO 1496/12-1, project number 548830090) and EPSRC (DJS, EP/V056069/1) is gratefully acknowledged, as well as the Alexander von Humboldt Foundation for awarding a postdoctoral fellowship to DJS.

Funding

Financial support by the DFG (RW, WO 1496/12-1, project number 548830090) and EPSRC (DJS, EP/V056069/1) is gratefully acknowledged, as well as the Alexander von Humboldt Foundation for awarding a postdoctoral fellowship to DJS.

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1039/d6dt01334aLicence: CC BY

Cite this

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title = "Closed-loop hydrostannylation of white phosphorus using Bu3SnCl and NaBH4: one-pot access to organophosphorus compounds",

abstract = "The direct functionalization of white phosphorus (P4) is gaining attention as an alternative to state-of-the-art multi-step processes. The hydrostannylation of P4 affords valuable monophosphorus compounds directly via a hydrostannylphosphine mixture (Bu3Sn)xPH3−x (where x = 0–3) that reacts with suitable electrophiles. However, previous reports required terminal reductants which are infeasible for industrial-scale applications. Here, we report an improvement in this chemistry using NaBH4 as the terminal reducing agent, generating the key hydrostannylation agent Bu3SnH in situ from Bu3SnCl. The resulting (Bu3Sn)xPH3−x mixtures were successfully functionalized towards useful P1 compounds. Furthermore, we present the {\textquoteleft}one-pot{\textquoteright} preparation of tetrakis(hydroxymethyl)phosphonium chloride (THPC), the subsequent direct recycling of Bu3SnCl, and preliminary attempts towards the catalytic synthesis of THPC.",

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