Diisopropyl diazomethylphosphonate

A more direct access to the unstable and non isolated sulfonium ylides 58a- c is the reaction of diisopropyl diazomethylphosphonate 57 with allylic sulfides, catalyzed by Cu(II), Rh(II) [39], or ruthenium porphyrins.[40] For example, the a-phosphorylated y,d-unsaturated sulfides 59-61 are obtained through the [2,3] -sigmatropic rearrangement of 58a-c. This method allows the use of a greater variety of starting allylic sulfide substrates, such as 2-vinyl tetrahydrothiophene, or propargylic sulfides (Scheme 15). 

The reaction conditions necessary in order to obtain, in high yields and pure form, either 1-cyanomethylphosphonates or 1-cyanomethylenediphosphonates, has been reported. Catalytic systems derived from Ru(CO) porphyrins are extremely efficient at converting styrene and diisopropyl diazomethylphosphon-ate to cyclopropyl phosphonate esters (172) in high yields and with high stereoselectivity. A monocarbene complex Ru(TPP)(CH P(0)(0iPr) 2) has been isolated as a possible catalytically active species. ... 

The catalytic effectiveness of ruthenium porphyrins for ylide generation in reactions of ethyl diazo acetate and diisopropyl diazomethylphosphonate with some allylic substrates was described for the first time by Simoimeaux and coworkers (Scheme 20) [194]. These reactions result in products of the [2,3]-sigmatropic rearrangement of intermediate allylic ylides. It was demonstrated that simple ruthenium porphyrins are highly effective catalysts for carbenoid reactions with alkyl allyl sulfides and alkyl allyl amines providing... 

Simonneaux and coworkers reported that chiral ruthenium porphyrin 270 was used for the asymmetric cyclopropanadon of diisopropyl diazomethylphosphonate [189] or... 

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