93222-05-0Relevant articles and documents
ABRAMOW-REAKTION VON KOHLENHYDRATDERIVATEN MIT FREIEN ANOMEREN ZENTREN
Thiem, Joachim,Guenther, Michael
, p. 67 - 80 (2007/10/02)
Diisopropylidene mannofuranose (1) and dimethylphosphite react under base catalysis in an Abramow reaction with subsequent internal transesterification to yield the diasteromeric δ-phostones 2, which are also transformed into their crystalline tosylates 3.Surprisingly these compounds adapt a boat conformation, however, after change of the protecting groups a flat chair conformation (of 8 and 9) results.The δ-phostone formation (7) turned out to be the preferred reaction course even when the cyclic phosphite 6 is applied to react with 1.In basic medium the tosylate 3 does not undergo a ring contraction to a glycosyl phosphonate, however the 2-desoxy mannonic acid ester 10 is obtained: this is discussed and a mechanism proposed.Starting with the ribofuranose derivative 12 the corresponding δ-phostones 14 are prepared.In the reaction of the glucopyranose compound 16 a competition between the formation of ε-phostones 19 and the open-chain phosphonates 21 is observed.