88897-28-3Relevant articles and documents
Approach to the Pseudodisaccharides Present in (Oxy)apramycin. Synthesis of a 4-O-Amino-octodiosyl-2-deoxystreptamine from Paromamine
Martin, Olivier R.,Szarek, Walter A.
, p. 926 - 928 (1983)
The synthesis of an N-protected 2'-amino-2'-deoxy-1'-O-(2-deoxystreptamin-4-yl)-α-D-threo-D-gluco-octo-1',5':4',8'-dipyranose in nine steps from paromamine is described; the key steps are the conversion of paromamine into a protected octuronic acid derivative, followed by its 8',4'-lactonization upon removal of the O-protecting groups, and partial reduction of the resulting 'trans-decalone-like' lactone.
SYNTHETIC ROUTES FROM PAROMAMINE TO THE OCTODIOSE-CONTAINING PSEUDODISACCHARIDE PRESENT IN (OXY)APRAMYCIN
Martin, Olivier R.,Szarek, Walter A.
, p. 195 - 220 (2007/10/02)
The synthesis of a 4-O-(2-amino-2-deoxyoctodiosyl)-2-deoxystreptamine, the first synthetic analog of the unusual pseudodisaccharide present in (oxy)apramycin was accomplished, starting from paromamine, by a two-carbon chain-elongation and a stereoselective cis-hydroxylation of the resulting E-unsaturated octuronate to give either ethyl 3,4-di-O-benzoyl-2-deoxy-2-p-tolylsulfonamido-D-threo-α-D-gluco- (12) or -L-threo-α-D-gluco-octo-1,5-pyranosid> uronate.Mehtoxide-mediated deacylation of 12 afforded in one step a bicyclic, trans-decalone-like urono-8',4'-lactone (14) that was highly sensitive to acid-catalyzed alcoholysis and had properties in sharp contrast to those of D-glucurono-6,3-lactone.Partial reduction of lactone 14 or of the corresponding methyl octuronate 12 with lithium aluminum hydride at low temperature gave the expected α-D-threo-D-gluco-octodialdo-1,5-pyranoside-8,4-pyranose, which was methanolyzed and N-detosylated to afford the free pseudodisaccharide 1-(2-deoxystreptamin-4-yl) 8-methyl (8R,S)-2-amino-2-deoxy-α-D-threo-D-gluco-octodialdo-1,5:8,4-dipyranodioside.All of the octodiose derivatives were found to adopt a rigid, dipyranoid structure.
