Streptose 3-deoxy-, synthesis

A chain-elongation reaction was used for the synthesis of streptose (167) starting from 5-deoxy-l,2-0-isopropylidene-j6-L-tAreo-pentofuranos-3-ulose (185).387... 

In addition to the functionalization protocols of Schemes 13 and 14, vinylic substitution reactions involving metalation and palladium-mediated carbon-carbon bond formation have been formulated," which further broaden the variety of stmctural types available from the Patemo-BUchi reaction. For example, deprotection and stannylation of photoaldol (133), followed by refimctionalization of the a-enol ether position of vinylstannane (134), gave the substituted oxetane (135) in good overall yield. Similar functionalization of bicyclic oxetane (136) via exo-face dihydroxylation and acid-catalyzed reorganization of the acetal to the protected 3-deoxy-( )-streptose (137) has been reported, which illustrates the synthetic utility of such processes in the synthesis of polyoxygenated materials." ... 

Whereas streptidine and 2-deoxy-2-(methylamino)-L-glucose, components of streptomycin, were synthesized by 1950, some fifteen years elapsed before the synthesis of streptose was achieved by Dyer and coworkers. Another synthesis of streptose was reported by Paulsen and coworkers. The glycosidic linkage between streptose and 2-deoxy-2-(methylamino)-L-glucose had previously been shown to be a-L, and the glycosidic linkage between streptose and streptidine has been revised to be o-L on the basis of n.m.r.-spectral studies. ... 

T. Kofluk and A. Zamojski, Hydroxylation of 6-substituted 2,7-dioxabicydo[3.2.0]hept-3-enes. The synthesis of analogs of 3-deoxy-DL-streptose," Collect. Czech. Chem. Commun., 48, 1659... 

An interesting synthesis of 3-deoxy-DL-streptose utilized the dioxabicycloheptene (30) obtained by cycloaddition of furan and ethanal stereospecific exo-cis-hydroxylation was accompanied by C-3 epimerization, giving a mixture resolved into the deoxy-... 

Bromo-2-deoxy-sugars, derived from glycals, can be photo-chemlcally converted into 2-deoxy-sugars on irradiation in 2-propanol thus compound (13) was obtained from bromide (1 ). Photolytic de-iodination was utilized in a synthesis of L-streptose (Chapter 13). 

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