高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

反式-2-取代硫代氨基脲基-4-芳基-5,5-二甲基-2-氧-1,3,2-二氧磷杂环己烷的立体选择性合成及立体化学研究

冯德鑫, 陈茹玉, 黄有   

  1. 南开大学元素有机化学研究所, 元素有机化学国家重点实验室, 天津 300071
  • 收稿日期:2005-12-19 修回日期:1900-01-01 出版日期:2006-12-10 发布日期:2006-12-10
  • 通讯作者: 陈茹玉

Stereoselective Synthesis and Study on the Stereochemistry of trans-2-Substituted-thiosemicarbazido-4-aryl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanes

FENG De-Xin, CHEN Ru-Yu, HUANG You   

  1. National Key Laboratory of Elemento-Organic Chemistry, Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
  • Received:2005-12-19 Revised:1900-01-01 Online:2006-12-10 Published:2006-12-10
  • Contact: CHEN Ru-Yu

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被引次数

1

摘要： 首先合成了重要的磷酰异硫氰酸酯中间体3, 然后便捷、高产率且立体选择性地合成了反式-2-取代硫代氨基脲基取代的新型六元磷杂环, 其立体化学通过2D NOESY NMR确证. 所有合成的化合物均进行了元素分析和光谱表征, 其中目标产物的13C NMR表征为1,3,2-二氧磷杂环己烷衍生物的碳骨架表征提供了难得的依据. 在溶剂DMSO-d6中, 所有产物均异构化, 生成磷原子的差向异构体. 这一研究结果证明了C4—H 以及31P NMR谱图与立体结构的相关性.

关键词: 1,3,2-二氧磷杂环己烷, 硫代氨基脲, 差向异构体

Abstract: 1,3,2-Dioxaphosphorinane derivatives are an important class of organophosphorus heterocycles, which continue to attract considerable interest due to their unique stereochemical features and diverse potential biological importance. It has been found that the stereochemistry is important for the bioactivities of 1,3,2-dioxaphosphorinane compounds. Therefore, there is still a need for the development of a more simple and convenient method for the stereoselective synthesis of 1,3,2-dioxaphosphorinane derivatives. In this article, novel trans-2-substituted-thiosemicarbazido-4-aryl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanes 5a—5j were synthesized via a series of reactions such as aldol-Cannizzaro, cyclization and addition and their structures are characterized by elemental analysis, 1H NMR, 13C NMR and 31P NMR. Their epimers at the phosphorus atom were found by the isomerization in DMSO-d6. This study gave a good explanation for the correlation between the configurational assignments and the chemical shifts of C4—H and 31P NMR.

Key words: 1,3,2-Dioxaphosphorinane, Thiosemicarbazide, Isomerization

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