Mitsunobu reaction glycoside synthesis

Roush WR, Lin X-F. Studies on the synthesis of aureolic acid antibiotics highly stereoselective synthesis of aryl 2-deoxy-p-glycosides via the Mitsunobu reaction and synthesis of the olivomycin A-B disaccharide. J. Am. Chem. Soc. 1995 117 2236 2250. 

The glycosylation based on the Mitsunobu reaction has been most commonly directed to the synthesis of O-aryl glycosides, a structural motif found in a variety of natural products [80-82], Early work by Grynkiewicz [83,84], among others [85-87], established the viability of triphenylphosphine and diethylazodicarboxylate to promote the glycosylation of phenol acceptors at ambient temperature. More recently, Roush and coworkers have discovered that the glycosylation performed well in the... 

Inversion of configuration (cf Epimerization) of alcohols (Mitsunobu reaction), 160-161, 286 of ally lie acetates with Pd, 27, 164 of allylpalladium with d-synthons, 27, 264 of alkyl halides or sulfonates by 1,3-dithiane anions, 22 by organylcuprates, 36 by tetracarbonylferrate<2 -X 46-47 in triorganylborane rearr., 37-38 of glycosides with free 2-OH by DAST, 272 of glycosyl halides, 271 of oxiranes by 1-alkync anions, 64, 204 by enolate type anions, 63-64 by internal alcoholate addition, 265 Inversion-esterification of alcohols, 160-161, 286 Inverted DNA , 345-346 Iodide, hydrogen porphyrin synthesis with, 255 Iodine = diiodine (Ij) ... 

Paterson reported a total synthesis of (+)-leucascandrolide A (199) in which essentially complete control over all of the stereochemistry is achieved. As outlined in Scheme 61, two Mitsunobu reactions were employed for macro-cyclization and installation of the side chain. The two ds-alkenes in the side chain were introduced by double Lindlar hydrogenation in the final stage. The oxygenated stereogenic centers on seco-acid 286 were constructed by reduction at C17 and C9, C-glycosidation at C15, and l,5-a ti-aldol reaction at Cll, all of which were by using substrate control. The 2,6-cis-tetrahydropyran in 287 was synthesized by the asymmetric hetero Diels-Alder reaction. 

A particular method for the anomeric activation of 1-hydroxy sugars is the Mitsunobu reaction which has mainly found application for the synthesis of aryl glycosides. Following from an earlier publication [66], Garegg described [67] the use of this reaction for synthesis of aryl p-o-mannopyranosides. Lubineau studied [68] the influence of the pKa of the acid or phenol in the formation of aryl and acylglyco-sides derived from three pesticides. 

MacDonald et al. introduced a new approach to glycoside synthesis using the tungsten-catalyzed ewJo-selective cycloisomerization of alkynol, which was easily prepared from a noncarbohydrate precursor. The alkynol substrate 161 was synthesized from 160 via sequential enantio-selective reduction and epoxidation, as well as the Mitsunobu reaction. The ewJo-selective cycloisomerization... 

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