For over half a century, thousands of tons of triphenylphosphine oxide Ph3P(O) have been produced every year from the chemical industries as a useless chemical waste. Here we disclose efficient transformations of Ph3P(O) with cheap resource-abundant metallic sodium finely dispersed in paraffin oil. Ph3P(O) can be easily and selectively transformed to three reactive organophosphorus intermediates—sodium diphenylphosphinite, sodium 5H-benzo[b]phosphindol-5-olate and sodium benzo[b]phosphindol-5-ide—that efficiently give the corresponding functional organophosphorus compounds in good yields. These functional organophosphorus compounds are difficult to prepare but highly industrially useful compounds. This may allow Ph3P(O) to be used as a precious starting material for highly valuable phosphorus compounds.

Sodium exhibits better efficacy and selectivity than Li and K for converting Ph3P­(O) to Ph2P­(OM). The destiny of PhNa co-generated is disclosed. A series of alkyl halides R4X and aryl halides ArX all react with Ph2P­(ONa) to produce the corresponding phosphine oxides in good to excellent yields.

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The original version of this Article contained an error in reference 2. The title in reference 2 was incorrectly written as 'The Staudinger ligation-a.pngt to chemical biology'. This error has been corrected in the HTML and PDF versions of the Article.