Phosphorylation, Perkow reaction

Borowitz, I.J., Yee, K.C., and Crouch, R.K., Determination of stereochemistry in vinyl phosphorylated species by nuclear magnetic resonance shift reagents. Revised mechanistic pathways for the Perkow reaction, /. Org. Chem., 38,1713, 1973. 

Gramine - 3-(dimethylaminomethyl)indole (14) - is a readily obtainable derivative of indole and is produced with a quantitative yield by the Mannich reaction. In [19] it was phosphorylated with diethyl chlorophosphite. 3-(Dimethylaminomethyl)-l-(triethoxyphosphito)indole (15) was obtained also by the method in [20] using diethyl penten-3-on-2-yl phosphite. Compound 15 readily adds sulfur with the formation of the corresponding gramine 1-thiophosphate 16 and reacts with chloral according to the scheme of the Perkow reaction, forming phosphate 17 ... 

This protocol is Whitesides and co-workers modification of Clark and Kirby s procedure.84,85 Dimethyl phosphoenolpyruvate 38 is synthesized on a large scale by the Perkow reaction and hydrolysed to potassium phosphoenolpyruvate 39, which may be used as a phosphorylating agent for the... 

Sekine, M., Nakajima, M., and Hata, T., Silyl phosphites. Part 16. Mechanism of the Perkow reaction and the Kukhtin-Ramirez reaction. Elucidation by means of a new type of phosphoryl rearrangements utilizing silyl phosphites, J. Org. Chem., 46, 4030, 1981. 

Borowitz and his co-workers have carried out a detailed comparative study of the reactions of phosphinites, phosphonites, and phosphites with -halogenoketones. The balance between keto-phosphorylation and enol-phosphorylation favours the former with increasing oxygen content of the phosphorus compound, higher temperature, more polar solvents, and bromo-rather than chloro-ketones. a -Dibromobiacetyl reacts with two moles of phosphite to give the double Perkow product (43) and no trace of the alternative Arbusov product or of the phosphorane (45). The rate of the first Perkow... 

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