高等学校化学学报

高等学校化学学报

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2’，4”-O-双(三甲基硅)-6-O-甲基红霉素A 9-O-(1-甲氧基环己基)肟的区域选择性合成机理及其晶体结构

梁建华, 姚国伟, 曹志凌, 甘强, 单春燕   

  1. 北京理工大学生命科学与技术学院, 北京100081
  • 收稿日期:2006-05-29 修回日期:1900-01-01 出版日期:2007-03-10 发布日期:2007-03-10
  • 通讯作者: 梁建华

Regioselective Synthesis Mechanism and Crystal Structure of 2’，4”-O-Bis(trimethylsilyl)-6-O-methylerythromycin A 9-O-(1-methoxycyclohexyl) oxime

LIANG Jian-Hua, YAO Guo-Wei, CAO Zhi-Ling, GAN Qiang, SHAN Chun-Yan   

  1. School of Life Science and Technology, Beijing Institute of Technology , Beijing 100081, China
  • Received:2006-05-29 Revised:1900-01-01 Online:2007-03-10 Published:2007-03-10
  • Contact: LIANG Jian-Hua

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摘要： 合成了化合物3的6-OH区域选择性甲基化产物, 即2',4"-O-双(三甲基硅)-6-O-甲基红霉素A 9-O-(1-甲氧基环己基)肟(4)的单晶, 以及化合物2的单晶, 并确定了其立体构型, 以期阐明区域选择性与大环内酯构象之间的关系.

关键词: 大环内酯, 区域选择性, 晶体结构

Abstract: 2',4"-O-Bis(trimethylsilyl) 6-O-methylerythromycin A 9-O-(1-methoxycyclohexyl) oxime was regioselectively synthesized and characterized and its crystal structure was determined by the single crystal X-ray structure analysis. The crystal belonged to tetragonal system with I4 space group and a=b=2.9720(4) nm, c=1.4939(3) nm, V=13.195(4) nm3, Z=8, R=0.0587, wR=0.1263, S=1.004 for 11526 unique reflections. The crystal structure shows that the attack of methylation reagents was blocked by 9-oxime ether as result, a hydrogen bond formed between 11-OH and nitrogen of 9-oxime, and the attack of methylation reagents was blocked by 9-oxime ether, whereas the orientation of 6-OCH3 was located in the cave surrounded by several rings so that 6-OH was unique one to be exposed to methylation reagents. However, the congestion around 11-OH was loosened, which resulted from the orientation of protective group so that much 6,11-O-dimethyl product was yielded. Additionally, the crystal structure of 2',4"-O-bis(trimethylsilyl) erythromycin A 9-O-(1-methoxy-1-methylethyl) oxime was first disclosed as a comparison.

Key words: Macrolide, Regioselectivity, Crystal structure

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