Suzuki E, Namba S, Kurihara H, Goto J, Matsuki Y, Nambara T
Hatano Research Institute, Food and Drug Safety Center, Kanagawa, Japan.
Steroids. 1995 Mar;60(3):277-84. doi: 10.1016/0039-128x(94)00054-g.
The synthesis of 15-N-acetylglucosaminides of 15 alpha-hydroxyesterone, 15 alpha-hydroxyestradiol, and 15 alpha-hydroxyestriol (estetrol) is described. The latter two were prepared by condensation of 2-acetamido-1 alpha-chloro-1,2-dideoxy-3,4,6-trio-O-acetyl-D-glucopyranose with appropriately protected 15 alpha-hydroxyestrogens by the Koenigs-Knorr reaction employing cadmium carbonate as a catalyst. Subsequent removal of protecting groups with methanolic potassium hydroxide provided the desired conjugates. 15 alpha-Hydroxyestrone 15-N-acetylglucosaminide was synthesized from the corresponding 15 alpha-hydroxyestradiol derivative by Jones oxidation followed by brief alkaline hydrolysis. These conjugates underwent enzymatic hydrolysis with beta-N-acetylglucosaminidase from Jack beans to produce 15 alpha-hydroxyestrogens.
描述了15α-羟基雌酮、15α-羟基雌二醇和15α-羟基雌三醇（雌四醇）的15-N-乙酰氨基葡萄糖苷的合成。后两者是通过采用碳酸镉作为催化剂的柯尼希斯-克诺尔反应，使2-乙酰氨基-1α-氯-1,2-二脱氧-3,4,6-三-O-乙酰基-D-吡喃葡萄糖与适当保护的15α-羟基雌激素缩合制备而成。随后用甲醇氢氧化钾除去保护基团，得到所需的缀合物。15α-羟基雌酮15-N-乙酰氨基葡萄糖苷由相应的15α-羟基雌二醇衍生物经琼斯氧化，然后进行短暂的碱性水解合成。这些缀合物用来自刀豆的β-N-乙酰氨基葡萄糖苷酶进行酶促水解，生成15α-羟基雌激素。
