103687-46-3Relevant articles and documents
A convenient route to the phosphorus and sulfur stereoisomers of ethyl menthyl (methylsulfinyl)methylphosphonate
Cardellicchio, Cosimo,Naso, Francesco,Capozzi, Maria Annunziata M.
, p. 1471 - 1476 (2007/10/03)
The four phosphorus and sulfur stereoisomers of ethyl menthyl (methylsulfinyl)methylphosphonate were obtained by preparing the corresponding sulfides from commercially available diethyl (methylthio)methylphosphonate and subjecting them to a highly diastereoselective hydroperoxide oxidation in the presence of catalytic amounts of a titanium (R)- or (S)-BINOL complex. The configuration at the sulfur stereogenic centre was assigned by a chemical correlation based upon a displacement reaction with Grignard reagents, whereas the configuration at the phosphorus stereogenic centre was assigned by taking advantage of a reaction sequence based upon the use of menthyl (R P)-methylphosphonothioic acid as a starting material.
STEREOCHEMISTRY OF SOME REACTIONS BETWEEN ALKYL S-METHYL METHYLPHOSPHONOTHIOATES AND CHIRAL ALKOXIDES
Hall, C. Richard,Inch, Thomas D.,Pottage, Colin,Williams, Nancy E.
, p. 4909 - 4918 (2007/10/02)
With R-(+) ethyl (or methyl) S-methyl methylphosphonothioate and (+)-pinacolyl alkoxide competitive and highly stereoselective displacements of O-alkyl and S-methyl occur, both reactions being with inversion of configuration.With the enantiomeric S-(-) ethyl (and methyl) S-methyl methylphosphonothioates and (+)-pinacolyl alkoxide the reactions, although still competitive, are no longer stereoselective.In contrast similar reactions with the sodium salt of (-)-menthol, (which might be considered to be the mirror image of (+)-pinacolyl alkoxide) occur highly stereoselectively with the S-(-) but not with R-(+) enantiomers.The displacement of O-alkyl from alkyl S-methyl methylphosphonothioates by ethoxide, pinacolyl alkoxide and menthyl alkoxide is not observed when methoxide is the nucleophile; in this case only displacement of S-alkyl group occurs.
