Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source

Zhizhou Liu, Alasdair I. Mckay, Lili Zhao, Craig M. Forsyth, Violeta Jevtović, Milena Petković, Gernot Frenking, Dragoslav Vidović

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7 Citations (Scopus)


Introducing a small phosphorus-based fragment into other molecular entities via, for example, phosphorylation/phosphonylation is an important process in synthetic chemistry. One of the approaches to achieve this is by trapping and subsequently releasing extremely reactive phosphorus-based molecules such as dioxophosphoranes. In this work, electron-rich hexaphenylcarbodiphosphorane (CDP) was used to stabilize the least thermodynamically favorable isomer of HO2P to yield monomeric CDP·PHO2. The title compound was observed to be a quite versatile phosphonylating agent; that is, it showed a great ability to transfer, for the first time, the HPO2 fragment to a number of substrates such as alcohols, amines, carboxylic acids, and water. Several phosphorous-based compounds that were generated using this synthetic approach were also isolated and characterized for the first time. According to the initial computational studies, the addition-elimination pathway was significantly more favorable than the corresponding elimination-addition route for "delivering"the HO2P unit in these reactions.

Original languageEnglish
Pages (from-to)7357–7365
Number of pages9
JournalJournal of the American Chemical Society
Issue number16
Publication statusPublished - 18 Apr 2022

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