(3l,4u)-di-tert-butyl <2-(tert-butyldimethylsiloxy)-3,4-dimethyl-1,5-hexadienyl>phosphonate | 131516-54-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (3l,4u)-di-tert-butyl <2-(tert-butyldimethylsiloxy)-3,4-dimethyl-1,5-hexadienyl>phosphonate
• 英文别名: [(1Z,3R,4S)-1-[bis[(2-methylpropan-2-yl)oxy]phosphoryl]-3,4-dimethylhexa-1,5-dien-2-yl]oxy-tert-butyl-dimethylsilane
• CAS: 131516-54-6
• 化学式: C₂₂H₄₅O₄PSi
• 分子量: 432.656
• InChiKey: XTTLZRZWHWBLPF-KLPGOZHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.13
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  di-tert-butyl <2-((E)-2'-butenyloxy)-1-butenyl>phosphonate 在 potassium hydride 、 双(三甲基硅烷基)氨基钾 、 lithium chloride 作用下， 以 四氢呋喃 、 二甲基亚砜 、 甲苯 为溶剂， 反应 31.5h， 生成 (3l,4u)-di-tert-butyl <2-(tert-butyldimethylsiloxy)-3,4-dimethyl-1,5-hexadienyl>phosphonate
  参考文献：
  名称：

  Carbanion-accelerated Claisen rearrangements. 7. Phosphine oxide and phosphonate anion stabilizing groups

  摘要：

  The utility of phosphine oxide and phosphonate groups has been examined in the context of the carbanion-accelerated Claisen rearrangement (CACR). Both of the groups permit the construction of substituted allyl vinyl ethers by allyl oxide addition to phosphorus-substituted allenes. Extensive optimization was required to suppress isomerization of both the allenes and the vinyl ethers. Using potassium dimsylate and lithium chloride as the base, both the phosphine oxides and phosphonates rearranged readily at room temperature with complete regioselectivity in good yield (62-93%). The phosphonates also showed a high level of diastereoselectivity (92% de). The characteristic features of the CACR were compared with the original arylsulfone version.

  DOI：

  10.1021/jo00003a021