2-{[(1Z,3S)-1-[dimethyl(phenyl)silyl]-4-methyl-1-penten-3-yl]oxy}-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide | 1378249-61-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-{[(1Z,3S)-1-[dimethyl(phenyl)silyl]-4-methyl-1-penten-3-yl]oxy}-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide
• 英文别名: (S)-(Z)-2-{[1-(dimethylphenylsilyl)-4-methylpent-1-en-3-yl]oxy}-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide
• CAS: 1378249-61-6
• 化学式: C₁₉H₃₁O₄PSi
• 分子量: 382.512
• InChiKey: FEZLBUABEMPNIY-MENFKHAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  25.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-{[(1Z,3S)-1-[dimethyl(phenyl)silyl]-4-methyl-1-penten-3-yl]oxy}-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide 、 9-phenethyl-9-bora-bicyclo[3.3.1]nonane 在 potassium methanolate 、 copper (I) acetate 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以95%的产率得到(E)-dimethyl(6-methyl-1-phenyl-4-hepten-3-yl)phenylsilane
  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：

  在 正丁基锂 、 四甲基乙二胺 、 二异丁基氢化铝 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 32.5h， 生成 2-{[(1Z,3S)-1-[dimethyl(phenyl)silyl]-4-methyl-1-penten-3-yl]oxy}-5,5-dimethyl-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

文献信息

• Functional Group Tolerable Synthesis of Allylsilanes through Copper-Catalyzed γ-Selective Allyl-Alkyl Coupling between Allylic Phosphates and Alkylboranes
  作者：Hirohisa Ohmiya、Masaya Sawamura、Kazunori Nagao

  DOI：10.1055/s-0031-1290818

  日期：2012.5

  A copper-catalyzed gamma-selective allyl-alkyl coupling between gamma-silylated allylic phosphates and alkylboron compounds (alkyl-9-BBN, prepared by hydroboration of alkenes with 9-BBN-H) produced allylsilanes. The reaction tolerated various functional groups in both the alkylboranes and the allylic phosphates, and afforded functionalized allylsilanes.