3-(3-dimethyl-tert-butylsilyl-2-hydroxymethylprop-2-enyl)-5-exo-hydroxy-ethylidene-1,1-dimethyl-2-oxa-1-silacyclopentane | 344357-99-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-(3-dimethyl-tert-butylsilyl-2-hydroxymethylprop-2-enyl)-5-exo-hydroxy-ethylidene-1,1-dimethyl-2-oxa-1-silacyclopentane
• 英文别名: (Z)-3-[tert-butyl(dimethyl)silyl]-2-[[(3Z)-3-(2-hydroxyethylidene)-2,2-dimethyloxasilolan-5-yl]methyl]prop-2-en-1-ol
• CAS: 344357-99-9
• 化学式: C₁₇H₃₄O₃Si₂
• 分子量: 342.626
• InChiKey: NUQJTGMGMGIGMW-FQSMVDRBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 3-(3-dimethyl-tert-butylsilyl-2-hydroxymethylprop-2-enyl)-5-exo-hydroxy-ethylidene-1,1-dimethyl-2-oxa-1-silacyclopentane 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以64%的产率得到5-(2-acetoxy-4-acetoxymethyl-5-tert-butyldimethylsilylpent-4-enyl)-1,1-dimethyl-2-oxa-1-silacyclopent-4-ene
  参考文献：
  名称：

  Novel DMAP-Catalyzed Skeletal Rearrangement of 5-exo-(2-Hydroxy- ethylene)oxasilacyclopentanes

  摘要：

  [GRAPHICS]5-exo-(Hydroxyethylene)-2-oxa-1-silacyclopentanes are found to undergo a novel DMAP-catalyzed skeletal rearrangement through silicon-oxygen exchange during acetylation to yield the corresponding 5-(2-acetoxyalkyl)-2-oxa-1-silacyclopent-4-enes exclusively. The mechanism for this unprecedented rearrangement is proposed.

  DOI：

  10.1021/ol016153o
• 作为产物：
  描述：

  t-butyldimethylsilane 在 acetylacetonatodicarbonylrhodium(l) sodium tetrahydroborate 作用下， 以 甲醇 、 甲苯 为溶剂， 50.0 ℃ 、1.01 MPa 条件下， 反应 24.75h， 生成 3-(3-dimethyl-tert-butylsilyl-2-hydroxymethylprop-2-enyl)-5-exo-hydroxy-ethylidene-1,1-dimethyl-2-oxa-1-silacyclopentane
  参考文献：
  名称：

  Desymmetrization of 4-Dimethylsiloxy-1,6-heptadiynes through Sequential Double Silylformylation

  摘要：

  [GRAPHICS]Desymmetrization of dimethylsilyloxyalkadiynes (1) by Rh-catalyzed intramolecular silylformylation affords 5-exo-(formylmethylene)-oxasilacyclopentanes 2 in high yields. Novel sequential double silylformylation of 1a also provides desymmetrization, giving 3-(3-silyl-2-formylprop-2-enyl)-5-exo-(formylmethylene)oxasilacyclopentanes 4 in excellent yields. Reduction of 2a and 4 with NaBH4 gives the corresponding 5-exo-(hydroxymethylmethylene)oxasilacyclopentanes 3a and 5, respectively.

  DOI：

  10.1021/ol0156594

文献信息

• Desymmetrization of 4-Dimethylsiloxy-1,6-heptadiynes through Sequential Double Silylformylation
  作者：Dominique Bonafoux、Iwao Ojima

  DOI：10.1021/ol0156594

  日期：2001.5.1

  [GRAPHICS]Desymmetrization of dimethylsilyloxyalkadiynes (1) by Rh-catalyzed intramolecular silylformylation affords 5-exo-(formylmethylene)-oxasilacyclopentanes 2 in high yields. Novel sequential double silylformylation of 1a also provides desymmetrization, giving 3-(3-silyl-2-formylprop-2-enyl)-5-exo-(formylmethylene)oxasilacyclopentanes 4 in excellent yields. Reduction of 2a and 4 with NaBH4 gives the corresponding 5-exo-(hydroxymethylmethylene)oxasilacyclopentanes 3a and 5, respectively.
• Novel DMAP-Catalyzed Skeletal Rearrangement of 5-<i>e</i><i>xo</i>-(2-Hydroxy- ethylene)oxasilacyclopentanes
  作者：Dominique Bonafoux、Iwao Ojima

  DOI：10.1021/ol016153o

  日期：2001.7.1

  [GRAPHICS]5-exo-(Hydroxyethylene)-2-oxa-1-silacyclopentanes are found to undergo a novel DMAP-catalyzed skeletal rearrangement through silicon-oxygen exchange during acetylation to yield the corresponding 5-(2-acetoxyalkyl)-2-oxa-1-silacyclopent-4-enes exclusively. The mechanism for this unprecedented rearrangement is proposed.