5,5-dimethyl-2-[(2Z,4S)-oct-2-en-4-yloxy]-1,3,2-dioxaphosphinane-2-oxide | 1378249-69-4

• 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: 5,5-dimethyl-2-[(2Z,4S)-oct-2-en-4-yloxy]-1,3,2-dioxaphosphinane-2-oxide
• 英文别名: 5,5-dimethyl-2-[(Z,4S)-oct-2-en-4-yl]oxy-1,3,2lambda5-dioxaphosphinane 2-oxide；5,5-dimethyl-2-[(Z,4S)-oct-2-en-4-yl]oxy-1,3,2λ5-dioxaphosphinane 2-oxide
• CAS: 1378249-69-4
• 化学式: C₁₃H₂₅O₄P
• 分子量: 276.313
• InChiKey: INPJKPOZQNJWRI-XYLWRLHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[4-(9-Borabicyclo[3.3.1]nonan-9-yl)butyl]-1,3-dioxane 、 5,5-dimethyl-2-[(2Z,4S)-oct-2-en-4-yloxy]-1,3,2-dioxaphosphinane-2-oxide 在 potassium tert-butylate 、 copper (I) acetate 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以80%的产率得到(E)-2-(5-methyl-6-undecen-1-yl)-1,3-dioxane
  参考文献：
  名称：

  Reversible 1,3-anti/syn-Stereochemical Courses in Copper-Catalyzed γ-Selective Allyl–Alkyl Coupling between Chiral Allylic Phosphates and Alkylboranes

  摘要：

  The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with gamma-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.

  DOI：

  10.1021/ja302520h
• 作为产物：
  描述：

  (S)-2-octyn-4-ol 在 二氯二茂钛 、 正丁基锂 、 四甲基乙二胺 、 ISOBUTYLMAGNESIUM BROMIDE 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 5,5-dimethyl-2-[(2Z,4S)-oct-2-en-4-yloxy]-1,3,2-dioxaphosphinane-2-oxide
  参考文献：
  名称：

  Reversible 1,3-anti/syn-Stereochemical Courses in Copper-Catalyzed γ-Selective Allyl–Alkyl Coupling between Chiral Allylic Phosphates and Alkylboranes

  摘要：

  The stereochemical courses of the copper-catalyzed allyl-alkyl coupling between enantioenriched chiral allylic phosphates and alkylboranes were switchable between 1,3-anti and 1,3-syn selectivities by the choice of solvents and achiral alkoxide bases with different steric demands. The reactions with gamma-silylated allylic phosphates allow efficient synthesis of enantioenriched chiral allylsilanes with tertiary or quaternary carbon stereogenic centers. Cyclic and acyclic bimodal participation of alkoxyborane species in an organocopper addition-elimination sequence is proposed to account for the phenomenon of the anti/syn-stereochemical reversal.

  DOI：

  10.1021/ja302520h