2,3,6,7,14,15-hexamethyl-9-phospha-10-stibatriptycene-9-oxide

• 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: 2,3,6,7,14,15-hexamethyl-9-phospha-10-stibatriptycene-9-oxide
• 化学式: C₂₄H₂₄OPSb
• 分子量: 481.178
• InChiKey: AOBNKLOIWQCFSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.75
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,3,6,7,14,15-hexamethyl-9-phospha-10 stibatriptycene 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 266.67h， 生成 2,3,6,7,14,15-hexamethyl-9-phospha-10-stibatriptycene-9-oxide
  参考文献：
  名称：

  (E)-带有 Phosphastibatriptycene 骨架的非稳定化鏻叶立德与苯甲醛之间的选择性 Wittig 反应

  摘要：

  苯甲醛衍生物与带有磷酸酯三萜骨架的不稳定鏻叶立德之间的 Wittig 反应，被视为三齿芳基配体，在锂盐和钠盐的存在下，产生具有高选择性的 (E)-烯烃。如前所述，三苯基鏻叶立德与苯甲醛衍生物在相同条件下的反应主要提供 (Z)-烯烃。变温 (VT) 31P{1H} NMR 光谱显示了两个信号，分配给顺式和反式 1,2-氧杂膦，它们在不同温度（分别为 –80 °C 和 –40 °C）下观察到在锂盐和钠盐存在的情况下，苯甲醛与带有磷酸三苯三烯骨架的不稳定鏻叶立德之间的 Wittig 反应表明，这些产物在 –40 °C 时存在平衡。另一方面，在三苯基鏻叶立德和苯甲醛之间的反应中没有清楚地观察到这种平衡，仅检测到一个信号。观察到的中间体通过分别带有 phosphastibatriptycene 骨架和三苯基膦部分的分离的 β-羟烷基鏻盐的去质子化证实为 1,2-oxaphosphetanes。在对氯苯甲醛存在下，β-羟烷基鏻盐与

  DOI：

  10.1002/ejoc.201601098

文献信息

• Heteroatom effects toward isomerization of intermediates in Wittig reactions of non-stabilized phosphonium ylides bearing a phosphaheteratriptycene skeleton with benzaldehyde
  作者：Yosuke Uchiyama、Suguru Kuniya、Ryo Watanabe、Takemaru Ohtsuki

  DOI：10.1002/hc.21473

  日期：2018.12

  AbstractIsomerization of intermediates, cis‐ and trans‐1,2‐oxaphosphetanes, in Wittig reactions of non‐stabilized phosphonium ylides bearing a phosphaheteratriptycene skeleton containing group 14 (PhSi, PhGe, PhSn, n‐BuSn) and 15 (P, As, Sb, and Bi) elements with benzaldehyde (PhCHO) was investigated by variable‐temperature (VT)31P1H} NMR spectroscopy. The isomerization from the cis‐1,2‐oxaphosphetane to the trans‐form occurred at lower temperatures as the row number of the same group elements increases. Wittig reactions under the same conditions gave the (Z)‐olefin as a major product in the cases of period 3 elements (PhSi and P) and the (E)‐olefin as a major product in the cases of elements from period 4 and below (PhGe, PhSn, n‐BuSn, As, Sb, and Bi). The selectivity of olefin formation is considered to depend on the isomerization temperature of the intermediates, because each olefin must be obtained from the corresponding 1,2‐oxaphosphetane. The VT‐31P1H} NMR spectra showed that the cis‐1,2‐oxaphosphetanes were the kinetic products in the first step of Wittig reactions and the trans‐forms were the thermodynamically stable products formed by isomerization from the cis‐forms via ring‐opening and ring‐closing reactions of phosphonium ylides with PhCHO. Density functional theory (DFT) calculations indicated that cis‐1,2‐oxaphosphetanes were less stable than the trans‐forms by ~2 kcal/mol, supporting thermodynamically favorable isomerization from cis‐forms to trans‐forms, as observed by VT‐31P1H} NMR spectroscopy. Heteroatoms at the bridgehead position of the phosphaheteratriptycene skeleton significantly affected the isomerization temperature as well as the phosphorus‐31 signals in the 31P1H} NMR spectra, which were observed at lower field as row number of the same group element increases.
• (<i>E</i> )-Selective Wittig Reactions between a Nonstabilized Phosphonium Ylide Bearing a Phosphastibatriptycene Skeleton and Benzaldehydes
  作者：Yosuke Uchiyama、Takemaru Ohtsuki、Rikiya Murakami、Munenori Shibata、Jun Sugimoto

  DOI：10.1002/ejoc.201601098

  日期：2017.1.3

  derivatives. These results clearly indicated that stereochemical drift occurred at those temperatures, even in reactions using nonstabilized phosphonium ylides. The stereochemical drift in the phosphastibatriptycene system occurred at a lower temperature than in the case of the triphenyl derivative, thus explaining the (E)-selective Wittig reactions between the benzaldehyde derivatives and the nonstabilized

  苯甲醛衍生物与带有磷酸酯三萜骨架的不稳定鏻叶立德之间的 Wittig 反应，被视为三齿芳基配体，在锂盐和钠盐的存在下，产生具有高选择性的 (E)-烯烃。如前所述，三苯基鏻叶立德与苯甲醛衍生物在相同条件下的反应主要提供 (Z)-烯烃。变温 (VT) 31P1H} NMR 光谱显示了两个信号，分配给顺式和反式 1,2-氧杂膦，它们在不同温度（分别为 –80 °C 和 –40 °C）下观察到在锂盐和钠盐存在的情况下，苯甲醛与带有磷酸三苯三烯骨架的不稳定鏻叶立德之间的 Wittig 反应表明，这些产物在 –40 °C 时存在平衡。另一方面，在三苯基鏻叶立德和苯甲醛之间的反应中没有清楚地观察到这种平衡，仅检测到一个信号。观察到的中间体通过分别带有 phosphastibatriptycene 骨架和三苯基膦部分的分离的 β-羟烷基鏻盐的去质子化证实为 1,2-oxaphosphetanes。在对氯苯甲醛存在下，β-羟烷基鏻盐与