Schmidt trichloroacetimidate

Schlosser s super base 615 f. Schmidt trichloroacetimidate glyco-sidation 528,531,537,556 Schwartz s reagent 606, 616 scopadulcic acid A 571 scopadulcic acid diterpenes 569 secocorrin 100, 122, 126 f., 130... 

Trichloroacetonitrile reacts with glycosidic hydroxy groups of protected sugars to form glycosyl trichloroacetimidates (R. R. Schmidt, 1980, 1984,1985,1986 B. Wegmann, 1988). The imidate is substituted by alcohols in the presence of trimethylsilyl trifluoromethanesulfonate... 

Danishefsky and co-workers described a regioselective formation of an oxazo-line 171 from a bis(trichloroacetimidate) 170 in their synthesis of staurosporine. The observed regioselectivity is apparently a result of a vinylogous Schmidt glycosylation (Scheme 8.49). 

J. Rademann and R. R. Schmidt, Solid-phase synthesis of a glycosylated hexapeptide of human sialophorin, using the trichloroacetimidate method, Carbohydr. Res. 269 217 (1995). 

R. R. Schmidt and J. Michel, Direct 0-glycosyl trichloroacetimidate formation. Nucleophilicity of the anomeric oxygen atom. Tetrahedron Lett. 25 821 (1984). 

H. Fisher, and R. R. Schmidt, Synthesis of unprotected 0-glycosyl trichloroacetimidates structure assignment and new results, Synlett, p. 84 (1994). 

Grundler, G. and Schmidt, R. (1984) Glycosyl imidates, 13. Application of the trichloroacetimidate procedure to 2-azidoglucose and 2-azidogalactose derivatives. Liebigs Ann. Chem., (11), 1826-1847. 

Schmidt, R. and Kinzy, W. (1994) Anomeric-oxygen activation for glycoside synthesis the trichloroacetimidate method. Adv. Carbohydr. Chem. Biochem. 50,21. 

Scheme 8.2 Control of anomeric selectivity in glycosidations via Schmidt s trichloroacetimidate method.

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