高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (5): 866.

• 研究论文 • 上一篇    下一篇

化学选择性还原21-叠氮基皮质激素法制备21-伯胺基皮质激素

彭久合, 李秉桀, 韩翀, 李祖成, 程津培   

  1. 南开大学化学系, 元素有机化学国家重点实验室, 天津 300071
  • 收稿日期:2003-04-24 出版日期:2004-05-24 发布日期:2004-05-24
  • 通讯作者: 程津培(1948年出生),男,博士,教授,博士生导师,中国科学院院士,从事物理有机和生物物理有机研究.E-mail:chengjp@mail.most.gov.cn E-mail:chengjp@mail.most.gov.cn
  • 基金资助:

    国家自然科学基金(批准号:29928004)资助

Chemoselective Reduction of 21-Azidocorticosteroids to Primary 21-Primary Aminocorticosteroids

PENG Jiu-He, LI Bing-Jie, HAN Chong, LI Zu-Cheng, CHENG Jin-Pei   

  1. State Key Lab of Elemental Organic Chemistry, Department of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2003-04-24 Online:2004-05-24 Published:2004-05-24

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被引次数

5

摘要： 以锌/氯化铵为还原剂,在含水四氢呋喃中将21-叠氮基皮质激素化学选择性地还原为21-伯氨基皮质激素.11β-羟基-21-叠氮基皮质激素比相应的11-酮基和11-去氧皮质激素容易还原,含水四氢呋喃是该反应的最适合溶剂,水的含量在还原体系中起着极其重要的作用.

关键词: 锌/氯化铵, 21-叠氮基皮质激素, 21-伯胺基皮质激素, 化学选择性还原

Abstract: The chemoselective reduction of 21-azidocorticosteroids to the corresponding 21-primary aminocorticosteroids was achieved with Zn/NH4Cl as a reductant in reasonable yields(70%—85%). 11β-Hydroxyl-21-azidocorticosteroids were found to be easier to reduced to their amino counterparts more easily than 11-carbonyl and 11-deoxyl-21-azides. Aqueous THF was found to be the most suitable solvent for this reaction, and the ratio of water in the reducing system was crucial. In THF of 95%—97% in volume fraction and at 15 ℃, Zn/NH4Cl can only reduce 11β-hydroxyl-21-azidocorticosteroids. To reduce the 11-carbonyl and 11-deoxy-21-azides, the volume fraction of water should be raised to 10% at least. This reduction method hasthe advantages of rather mild conditions, cheap and easily accessible reagents, and reasonable overall yields. Moreover, its simple work up and easy manipulation in large scale make our method superior to the reported Gabriel and 21-aldehyde oxime reduction procedures in the literature.

Key words: Zinc/ammonium chloride, 21-Azidocorticoids, 21-Primary aminocorticoids, Chemoselective reduction

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