Z-cyclooct-2-enyltriphenylstannane | 133816-70-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Z-cyclooct-2-enyltriphenylstannane
• CAS: 133816-70-3
• 化学式: C₂₆H₂₈Sn
• 分子量: 459.218
• InChiKey: XVHVWXYWWJUHGR-SQDRRJMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.05
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  顺-环辛烯 、 三苯基氯化锡 在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 生成 Z-cyclooct-2-enyltriphenylstannane
  参考文献：
  名称：

  Characterization of (Z)-cyclooct-2-enylstannanes

  摘要：

  (Z)-Cyclooct-2-enyltrimethylstannanes and -triphenylstannanes have been synthesized and characterized by H-1 and C-13 NMR spectra, which indicate a predominating unsymmetrical chair-boat arrangement. A mixture of the cis and trans isomers of both the (4-methylcyclooct-2-enyl)- and (8-methylcyclooct-2-enyl)trimethylstannanes (allylic stannanes) results from a sequence commencing with methylcyanocuprate opening of the monoepoxide of 1,3-cyclooctadiene, which is considered to afford regio- and stereoselectively trans-4-methylcyclooct-2-enol. Chlorination of this alcohol with both thionyl chloride and N-chlorosuccinimide/dimethyl sulfide has been conducted and the structures of the chlorides established by NMR methods and use of [1-H-2(1)]-4-methylcyclooct-2-enol. Trimethylstannylation of the chloride mixtures provides the four possible allylic stannanes, with one of the rearranged 8-methyl isomers slightly predominating. NMR spectra of various fractions from preparative gas chromatography have been obtained, and full assignment of the C-13 NMR spectra of the isomers is reported. Acidolysis of these fractions (with CF3COOD) proceeds rapidly to yield mixtures of H-2-substituted 3- and 4-methylcyclooctenes, but only one diastereomer of each system appears to be formed, on the basis of the C-13 NMR spectra. This implies that electrophile approach to the pi-face at the gamma-carbon is not influenced by the orientation of the C-Sn bond but is probably dictated by the predominant molecular conformation.

  DOI：

  10.1021/om00051a022