Anomeric C19-steroid N-acetylglucosaminides

Abstract

the spectrum of 11; mass spectrum (70 eV, glpc inlet, ion source 230') ( Figure 6).Jones Oxidation of .-Jones reagent14 (8 N , 0.85 ml) was added dropwise to a solution of 1.125 g (2.92 mmol) of alcohol 4 in 100 ml of acetone a t 20'. The solution was warmed to room temperature and then diluted with an equal volume of water. The ether extract of this solution was washed with water (twice), saturated sodium bicarbonate solution, and brine. Evaporation of the solvent and crystallization from acetone ave0.9 g (81%) of pure cholest-5-en-4-one6: mp 111-112'; /.r (6 AZFo 241 m M (e 6000) [lit.I5 mp 111-112'; A~~o f " 241 m 7200)l; Y: : : "1675 and 1620 cm-l. Reaction of Sodium Hydride with 3p-p-Toluenesulfonoxycholest-5-en+-01 (I).--To a stirred solution of 500 mg (0.9 mmol) of tosylate 1 in 25 ml of tetrahydrofuran (thf) under a nitrogen atmosphere was added 41.0 g (0.9 mmol) of sodium hydride on mineral oil 52.8% NaH). The mixture waa heated at reflux for 3 hr, cooled, and 1 equiv of water was added dropwise. The resulting solution was filtered and evaporated to dryness a t reduced pressure. The brown residue which resulted was dissolved in ether and the ether solution was washed with water (twice), 5% sodium bicarbonate, and brine, and then dried over sodium sulfate. Evaporation of the solvent gave 0.45 g of crude %

Steroid conjugates. VII. Preparation of N-acetylglucosaminides of 17α- and 17β-estradiol

“…The values of the estradiol anomers described herein are in agreement with their published data, the a anomer having a very positive rotation value, and the [M]D ( -ß) having a range of +400 to +700 (see Table I). Certain nuclear magnetic resonance chemical shifts and coupling constant values for the CTH which show a difference between the axial proton of the ß anomer and the equatorial proton of the a anomer, are also given in this paper (Sauer et al, 1969). Here also our results were in agreement with the published data (see Table II).…”

“…Usually, Koenigs-Knorr (1901) condensations have been performed in the presence of silver carbonate, silver oxide, etc. In a recent publication by Sauer et a!. (1969) salts such as mercuric chloride and mercuric cyanide have been used.…”

“…The structural assignment given to the glycoside, anomers was based on rotational and nuclear magentic resonance data. Sauer et al (1969) prepared a series of C-19 steroid a-and ßperacetylated glucosaminides, and calculated the molecular rotation differences in the anomeric pairs. The values of the estradiol anomers described herein are in agreement with their published data, the a anomer having a very positive rotation value, and the [M]D ( -ß) having a range of +400 to +700 (see Table I).…”

Configuration of naturally occurring steroid 2-acetamido-2-deoxy-D-glucosides

“…Young, D. G., and Hall, P. F. (1968a), Endocrinology 82,291. On the Configuration of Naturally Occurring Steroid M-Acetylglucosaminides* Michio Matsuij" and David K. Fukushima abstract : Synthesis of 3/3-hy droxy-5-pregnen-20a-yl 2'acetamido-2'-deoxy-/3-D-glucopyranoside and the anomers of 3/3-hydroxy-5a-pregnan-20a-yl 2 '-acetamido-2 '-deoxy-Dglucopyranoside has provided evidence for the assign-T A he synthesis of the anomeric pair of 2-acetamido-2deoxy-D-glucopyranoside of Ci9 steroids conjugated at C-3 or at C-17 has been recently accomplished (Sauer et al, 1969).…”

“…It has been well established that the Koenigs-Knorr reaction leads almost exclusively to /3-glycosides. A-Acetyl-/3-oglucosaminides of Ci9 steroids have recently been prepared by this method (Sauer et al, 1969). Thus condensation of 5a-pregnane-3/3,20a-diol 3-monoacetate and la-chloro-2acetamido-2-deoxy-3,4,6-tri-0-acetyl-D-glucopyranose with mercuric salts afforded 3/3-acetoxy-5a-pregnan-20a-yl 2'acetamido-2 '-deoxy-3 ',4 ',6 '-tri-0-acetyl-/3-D-glucopyranoside (Ha).…”