2-Ethyl-2-phosphabicyclo[2.2.2]oct-7-ene derivatives: Synthesis and use in fragmentation-related phosphorylations

Szelke, H.; Bálint, Ágnes; Király, Erzsébet; Ludányi, Krisztina; Kovács, János; Keglevich, György

doi:10.1002/hc.20093

Cited by 12 publications

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“…According to another protocol, phosphabicyclo[2.2.2]octadieneor -octene derivatives served as the precursors of methylenephosphine oxides giving the phosphinates by phosphorylation of the alcohols or phenols. The fragmentation was achieved photo chemically or thermally (Scheme 16) [85][86][87][88][89][90][91][92].…”

Section: Scheme 15mentioning

confidence: 99%

Synthesis of Phosphinic Acid Derivatives; Traditional Versus up-to-Date Synthetic Procedures

Keglevich

Kiss²,

Mucsi³

2014

Chem Sci J

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Synthetic methods for the preparation of phosphinic derivatives (esters and amides) are summarized. The basic method is, when phosphinic chlorides are reacted with alcohols or amines. These reactions take place under mild conditions, but utilize expensive chlorides, need a solvent, and a base has to be added to remove the HCl formed. On conventional heating, the phosphinic acids resist undergoing derivatizations by nucleophiles. However, on microwave (MW) irradiation, the phosphinic acids could be esterified by alcohols. The direct esterification does not require an extra solvent, it is atomic efficient, but needs a relatively higher temperature. The similar amidations were reluctant. Phosphinic acids may also be esterified by alkylation that may be promoted by combined phase transfer catalysis and MW irradiation. It is also possible to convert the phosphinic acids by different reagents (e.g. by the T3P  reactant) to a more reactive intermediate that is ready to react with alcohols or amines. Other methods, such as preparation by the Arbuzov reaction or by fragmentation-related phosphorylation are also discussed.

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