Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany.
Nat Chem. 2021 May;13(5):458-464. doi: 10.1038/s41557-021-00657-7. Epub 2021 Apr 5.
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 (P) 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 P. Reduction of P 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 PH, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride.
由于在制药、光引发剂和催化剂配体等众多应用中发挥着关键作用，单磷化合物具有巨大的工业重要性。白磷（P）是制备所有此类化学品的关键起始材料。然而，目前的生产依赖于间接的、低效的多步工艺。在这里，我们报告了一种简单、有效的“一锅法”，可直接从 P 制备各种有机和无机单磷物种。使用三丁基锡氢化物还原 P，然后用各种亲电试剂处理，可得到对化学工业具有关键重要性的化合物，而且仅需要温和的条件和廉价、易于处理的试剂。至关重要的是，我们还展示了三丁基锡试剂的简便高效的回收和最终的催化用途，从而避免了形成大量含 Sn 的废物。可获得的、工业相关的产品包括熏蒸剂 PH、还原剂次磷酸和阻燃剂前体四羟甲基氯化磷。
