Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO 2 P Source

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2022-04, Vol.144 (16), p.7357-7365
Main Authors: Liu, Zhizhou, McKay, Alasdair I, Zhao, Lili, Forsyth, Craig M, Jevtović, Violeta, Petković, Milena, Frenking, Gernot, Vidović, Dragoslav
Format: Article
Language:English
Subjects:
Alcohols
Amines
Carboxylic Acids - chemistry
Phosphorus
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Summary: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 ( ) was used to stabilize the least thermodynamically favorable isomer of HO P to yield monomeric . 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 HPO 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 HO P unit in these reactions.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.2c00936