Allyl phosphoryl compounds

In an analogous reaction to that of sulfenates, unsaturated esters of P compounds rearrange easily (equation 24) to corresponding allyl- and allenyl-phosphoryl compounds because the strong heteroatom-oxygen double bond is formed (Scheme 31). ... 

Phosphoryl diazomethanes react with 2,6-di-/erf-butylthiopyrylium ion (26) in the presence of triethylamine to give the corresponding 4-(di-azomethyl)-4//-thiopyrans 349-353. Reaction of compound 349 or 350 with di-/x-chlorobis-(7r-allyl)palladium(Il), instead of the expected thiepine derivative, afforded the anhydrobase 354 or 355, respectively (85T811). 

Ahlbrecht, H., Farnung, W., and Simon, H., Formation and reactivity of 1-phosphoryl-l-(phosphoryl-oxy)allyl anions and related compounds, Chem. Ber., 117, 2622, 1984. 

Synthesis of Phosphoric Acids and Their Derivatives. - A series of monoalkyl and dialkyl phosphorus acid chiral esters have been synthesised for use as carriers for the transport of aromatic amino acids through supported liquid membranes. The compounds acted as effective carriers but enantio-separation was at best moderate. A range of phosphono- and phosphoro-fluoridates have been prepared by treatment of the corresponding thio- or seleno- phosphorus acids with aqueous silver fluoride at room temperature (Scheme 1). In some cases oxidation rather than fluorination occurred. Stereospecifically deuterium-labelled allylic isoprenoid diphosphates, e.g. (1), have been synthesised from the corresponding deuterium-labelled aldehyde by asymmetric reduction, phosphorylation and Sn2 displacement with pyrophosphate (Scheme 2). ... 

From the previous paragraphs, it would appear that, under controlled conditions, it might be possible to effect a change in the hybridization of carbon bonded directly to phosphorus through the use of allylic phosphonates or related compounds and, indeed, it has been claimed that the phosphorylation of diethyl allylphosphonate itself can be used to prepare the propenylidene-l,l-bisphosphonic ester 350 (Scheme 45)". ... 

This result would appear to be at variance with the more complex picture presented later by Chinese workers. The latter" showed that when the allylic phosphonates 351 were converted into their carbanions with Ida in thf, and phosphorylated with diethyl phos-phorochloridate, the phosphorylation reaction occurred at the a-carbon to give 352, and the latter were also formed from the similar treatment of 353 when, however, hmpa was added to the solvent for the first of these two reactions, the products then consisted of two different compounds, 354 and 355, in the ratio 4 1. The difference in the reaction outcome... 

The 4-and 5-phosphates of KDO have been prepared as their O-allyl glycosides by phosphorylation of the 7,8-0-isopropylidene methyl ester and separation of the two regioisomers. Various methyl glycosides of KDO phosphorylated at 0-4 and alkylated at 0-5, as in the case of (43), have been made to assist in the identification of KDO derivatives isolated naturally. When the glycosidic link is hydrolysed, such compounds undergo elimination of phosphate, and, if possible, subsequent Michael-type intramolecular... 

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