2-methyl-2-(3-phenyldimethylsilyl)propyl-5,5-dimethyl-1,3-dioxane | 133930-59-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-(3-phenyldimethylsilyl)propyl-5,5-dimethyl-1,3-dioxane
• 英文别名: Dimethyl-phenyl-[3-(2,5,5-trimethyl-1,3-dioxan-2-yl)propyl]silane；dimethyl-phenyl-[3-(2,5,5-trimethyl-1,3-dioxan-2-yl)propyl]silane
• CAS: 133930-59-3
• 化学式: C₁₈H₃₀O₂Si
• 分子量: 306.521
• InChiKey: GFDDWXKBOKETDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.17
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  苯基二甲基氯硅烷 在 lithium methyl(cyano)cuprate 、 lithium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.5h， 生成 2-methyl-2-(3-phenyldimethylsilyl)propyl-5,5-dimethyl-1,3-dioxane
  参考文献：
  名称：

  The composition and chemistry of the mixed higher-order cuprates (PhMe2Si)m(CH3)nCu(CN)Li(m+n)

  摘要：

  Low-temperature Si-29, C-13, and H-1 NMR spectroscopic techniques were used to probe the nature of THF solutions of cuprates derived from PhMe2SiLi, MeLi, and CuCN in the stoichiometric ratios 1:1:1, 2:1:1, and 1:2:1 (Si:Me:Cu). Unlike the corresponding mixed stannyl systems that yield R3Sn(R)2CuLi2 when the ratio of stannyl anion:alkyl anion:cuprous ion is 1:2:1, these mixed silyl systems only form R3Si(R)Cu(CN)Li2. Solutions wherein the ratio of silyl anion and alkyl anion to cuprous ion is greater than 2:1 contain alkyllithium uncoordinated with cuprous ion. The most striking result is the preferential displacement of RLi when R3SiLi is added to solutions of R3Si(R)Cu(CN)Li2 or R2Cu(CN)Li2. These mixed metallocuprate solutions preferentially transfer the PhMe2Si moiety in reactions with alpha,beta-unsaturated enones and other unsaturated organic substrates. However, the mixed alkylsilylcuprate (PhMe2Si)(CH3)Cu(CN)Li2 reacts with 1,2-epoxyoctane to afford up to 31% of the methylated alcohol. Frontier orbital analysis of both the predominant cuprates species and preferential ligand transfer provides a rationale for the observed behavior.

  DOI：

  10.1021/jo00011a013

文献信息

• The composition and chemistry of the mixed higher-order cuprates (PhMe2Si)m(CH3)nCu(CN)Li(m+n)
  作者：Robert D. Singer、Allan C. Oehlschlager

  DOI：10.1021/jo00011a013

  日期：1991.5

  Low-temperature Si-29, C-13, and H-1 NMR spectroscopic techniques were used to probe the nature of THF solutions of cuprates derived from PhMe2SiLi, MeLi, and CuCN in the stoichiometric ratios 1:1:1, 2:1:1, and 1:2:1 (Si:Me:Cu). Unlike the corresponding mixed stannyl systems that yield R3Sn(R)2CuLi2 when the ratio of stannyl anion:alkyl anion:cuprous ion is 1:2:1, these mixed silyl systems only form R3Si(R)Cu(CN)Li2. Solutions wherein the ratio of silyl anion and alkyl anion to cuprous ion is greater than 2:1 contain alkyllithium uncoordinated with cuprous ion. The most striking result is the preferential displacement of RLi when R3SiLi is added to solutions of R3Si(R)Cu(CN)Li2 or R2Cu(CN)Li2. These mixed metallocuprate solutions preferentially transfer the PhMe2Si moiety in reactions with alpha,beta-unsaturated enones and other unsaturated organic substrates. However, the mixed alkylsilylcuprate (PhMe2Si)(CH3)Cu(CN)Li2 reacts with 1,2-epoxyoctane to afford up to 31% of the methylated alcohol. Frontier orbital analysis of both the predominant cuprates species and preferential ligand transfer provides a rationale for the observed behavior.