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有机化学 ›› 2011, Vol. 31 ›› Issue (12): 2145-2150. 上一篇    下一篇

研究简报

(1R,5S)-3-羟基二环[3.1.0]己基-6-基(苯基)甲酮的合成及其Norrish Ⅱ型光化学反应研究

张成路*，周龙，李元东，邵懿，高丽娜，曲瑞峰，徐德青   

  1. (辽宁省生物技术与分子药物研发重点实验室 辽宁师范大学化学化工学院 大连 116029)
  • 收稿日期:2011-03-23 修回日期:2011-06-15 发布日期:2011-08-15
  • 通讯作者: 张成路 E-mail:zhangchenglu@lnnu.edu.cn

Synthesis of (1R,5S)-3-Hydroxybicyclo[3.1.0]hexan-6-yl(phenyl)- methanone and Its Application in Norrish Type II Photochemical Reaction

ZHANG Cheng-Lu, ZHOU Long, LI Yuan-Dong, SHAO Yi, GAO Li-Na, QU Rui-Feng, XU De-Qing   

  1. (Liaoning Provincial Key Laboratory of Biotechnology and Drug Discovery, School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029)
  • Received:2011-03-23 Revised:2011-06-15 Published:2011-08-15

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以二环[3.1.0]己烷为骨架设计了合理的合成路线, 成功合成了具有Norrish II型光化学特点的光化学反应前体(1R,5S)-3-羟基-6-二环[3.1.0]己基苯基甲酮(10), 并通过1H NMR, 13C NMR, DEPT135, H-H COSY, HMQC, HMBC, ROESY, 6-H-1D-NOE, 9-H-1D-NOE和HRMS等方法表征了该化合物的结构, 确定了其绝对构型. 应用Norrish II型光化学反应, 以10为底物探索了重要前列腺素中间体化合物11的合成. 通过综合谱图表征和HPLC等手段测试, 结果表明化合物10经过Norrish II型光化学反应得到了两个具有环戊烯结构的光化学产物化合物11和12, 并据此提出了反应机理.

关键词: 二环[3.1.0]己烷, Norrish II型光化学反应, 前列腺素体

A reasonable synthetic route was designed based on bicyclo[3.1.0]hexane skeleton. Norrish II type photochemical precursor (1R,5S)-3-hydroxybicyclo[3.1.0]hexan-6-yl(phenyl)methanone (10) was successfully synthesized. The absolute configuration of 10 was determained by means of 1H NMR, 13C NMR, DEPT135, H-H COSY, HMQC, HMBC, ROESY, 6-H-1D-NOE, 9-H-1D-NOE and HRMS. Meanwhile, the important intermediate 11 of pros-taglandins (PG) was afforded through Norrish II type photochemical reaction using 10 as substrate. As a result, 11 and 12 which possess cyclopentene structure were obtained through the characterization of NMR and HPLC. The mechanism of the photochemical reaction was also put forward.

Key words: bicyclo[3.1.0]hexane, Norrish II type photochemical reaction, prostaglandin

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