Selective synthesis of 4-methoxyestrogen from 4-hydroxyestrogen.
The introduction of an oxygen atom into the C-6 position of 4-hydroxyestrogen allowed for the selective methylation of the two phenolic hydroxyl groups. When the 6-oxo derivative of 4-hydroxyestrone was benzylated in ethanol, only the 3-monobenzyl ether was obtained without formation of the 4-monobenzyl ether. Moreover, the 6-carbonyl group was further reduced to methylene almost quantitatively in the reaction of 4-acetoxy-6-oxoestrone 3-benzyl ether derivative with sodium borohydride. Therefore, 4-methoxyestrogen was synthesized by essentially combining these two reactions.
Teranishi
M
M
Faculty of Pharmaceutical Sciences, Hokuriku University, Ho-3, Kanagawa-machi, 920-1181, Kanazawa, Japan. m-teranishi@hokuriku-u.ac.jp
Kashihara
M
M
Fujii
Y
Y
D004958:Estradiol / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D004967:Estrogens / Q000737:chemistry; D002393:Estrogens, Catechol / Q000737:chemistry; D006838:Hydrocarbons; D008697:Methane / Q000031:analogs & derivatives* / Q000378:metabolism; D008745:Methylation; D013696:Temperature
D004967:Estrogens; D002393:Estrogens, Catechol; D006838:Hydrocarbons; C030011:carbene; C045018:4-methoxyestradiol; D004958:Estradiol; C014036:4-hydroxyestradiol; D008697:Methane