A concise enantioselective entry to the synthesis of deoxy-azasugars.
[reaction: see text] A concise enantioselective preparation of oxazolidinylpiperidine 4, a key intermediate in the synthesis of glycosidase inhibitors such as 1-deoxymannojirimycin or 1-deoxygalactostatin, has been developed. Sharpless catalytic asymmetric epoxidation of (E)-2,4-pentadienol followed by treatment with allyl isocyanate afforded epoxy carbamate 8. Regioselective intramolecular ring opening promoted by sodium bis(trimethylsilyl)amide and ring-closing metathesis provided the bicyclic intermediate 4 in high enantiomeric purity. The four-step sequence takes place in 51% overall yield.
Martín
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R
Departament de Química Orgànica, Universitat de Barcelona, Spain. are@ursa.qo.ub.es
Moyano
A
A
Pericàs
M A
MA
Riera
A
A
D017485:1-Deoxynojirimycin / Q000138:chemical synthesis; D001372:Aza Compounds / Q000138:chemical synthesis* / Q000494:pharmacology; D003837:Deoxy Sugars / Q000138:chemical synthesis* / Q000494:pharmacology; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D005688:Galactosamine / Q000031:analogs & derivatives / Q000138:chemical synthesis; D006026:Glycoside Hydrolases / Q000037:antagonists & inhibitors*; D015394:Molecular Structure; D010880:Piperidines / Q000138:chemical synthesis / Q000494:pharmacology; D013237:Stereoisomerism
D001372:Aza Compounds; D003837:Deoxy Sugars; D004791:Enzyme Inhibitors; D010880:Piperidines; C051195:5-amino-5-deoxygalactopyranose; D017485:1-Deoxynojirimycin; D005688:Galactosamine; D006026:Glycoside Hydrolases