ANOMERIC C-19-STEROID N-ACETYLGLUCOSAMINIDES

The α and β anomers of C-19-steroid 2′-acetamido-2′-deoxy-D-glucopyranoside conjugated at C-3 or C-17 have been prepared from their corresponding 3′,4′,6′-tri-O-acetyl derivatives. The acetylated β-glucosaminides were synthesized from the steroid and 1α-chloro-2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-D-glucopyranose with mercuric salts; anomerization was achieved by treatement of the acetylated β-glucosaminides with titanium tetrachloride. The differences in the molecular rotation and ir and nmr spectra between the anomers were studied. The α anomer had a sharply defined intense band between 1110 and 1125 cm-1 whereas the β anomer lacked this strong absorption between 1100-1200 cm-1. In addition to the difference of the splitting patterns of the anomeric H-1′ protons in the nmr spectra, a broad multiplet for the H-6′ methylene protons, W1/2 ~ 8.5 cps, in the β anomer and a narrow multiplet, W1/2 ~ 4.0 cps, in the a anomer at δ 4.1-4.2 ppm were observed. For comparison purposes the synthesis and physical properties of the anomers of cyclohexyl N-acetylglucosamimdes were investigated. © 1969, American Chemical Society. All rights reserved.