高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (3): 489.doi: 10.7503/cjcu20140798

• 有机化学 • 上一篇    下一篇

2-苯基/环己基环十二酮的还原选择性及trans-1,2-二取代环十二烷的构象分析

杨明艳, 张莉, 王道全, 王明安()   

  1. 中国农业大学应用化学系, 北京100193
  • 收稿日期:2014-09-03 出版日期:2015-03-10 发布日期:2015-01-30
  • 作者简介:联系人简介: 王明安, 男, 博士, 教授, 博士生导师, 主要从事有机合成及新农药创制研究. E-mail: wangma@cau.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21172254)资助

Reduction Selectivity of 2-Substituted Cyclododecanone and Conformation Analysis of trans-1,2-Disubstituted Cyclododecanes

YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming'an*()   

  1. Department of Applied Chemistry, China Agricultural University, Beijing 100193, China
  • Received:2014-09-03 Online:2015-03-10 Published:2015-01-30
  • Contact: WANG Ming'an E-mail:wangma@cau.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21172254)

摘要:

通过研究2-苯基/环己基环十二酮在不同还原剂和温度下的还原反应证实了2-取代环十二酮的还原反应具有cis-选择性. 在此基础上, 通过2-取代环十二酮的NaBH4还原反应、 1,2-环氧环十二烷的开环反应及cis-2-苯基环十二醇的Mitsunobu反应和水解反应制备了一系列trans-1,2-二取代环十二烷; 采用 1H NMR、 13C NMR、 X射线衍射和量子化学计算等方法对其优势构象进行了分析. 结果表明, trans-1,2-二取代环十二烷的优势构象为[3333]方形构象, 1个取代基位于边碳外向位(Side-exo), 另1个位于角碳反向位(Corner-anti). cis-2,12-二取代环十二酮的LiAlH4还原产物的X射线衍射分析结果表明, 生成的1,2,3-三取代环十二烷保持了环十二烷的[3333]方形构象, 2个取代基位于边碳外向位, 羟基位于角碳顺向位(Corner-syn), 取代基呈现出cis-cis关系.

关键词: 2-苯基/环己基环十二酮, trans-1,2-二取代环十二烷, 1,2,3-三取代环十二烷, 构象分析

Abstract:

To confirm the cis-selectivity on the reduction of 2-substituted cyclododecanone and analyze the preferred conformation of trans-1,2-disubstituted cyclododecanes, the reduction of 2-phenyl/cyclohexylcyclododecanones were carried out at the different reductive reagents and temperatures. Based on these results, a series of trans-1,2-disub- stituted cyclododecanes was prepared via NaBH4 reduction of 2-substituted cyclodode- canones, ring-opening of cyclododecene oxide, Mitsunobu reaction of cis-2-phenyl cyclododecanol and hydrolysis, their preferred conformation were analyzed on the basis of 1H NMR, 13C NMR, X-ray diffraction and quantum chemistry calculation. The results showed that the preferred conformations of trans-1,2-disubstituted cyclododecanes were [3333] square conformation, in which the one group presents at the side-exo position and the other one at the corner-anti. The X-ray diffraction structures of the reductive products of cis-2,12-disubstituted cyclododecanones showed that 1,2,3-trisubstituted cyclodode- canes still take [3333] square conformation, in which the two groups present at the side-exo positions and the hydroxy at the corner-syn, three groups are cis-cis relationships.

Key words: 2-Phenyl/cyclohexylcyclododecanone, trans-1,2-Disubstituted cyclododecane, 1,2,3-Trisubstituted cyclododecane, Conformation analysis

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