5-butyl-1-(triisopropylsilyl)nona-1,3-diyn-5-ol | 503570-04-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-butyl-1-(triisopropylsilyl)nona-1,3-diyn-5-ol
• 英文别名: 5-butyl-1-tri(propan-2-yl)silylnona-1,3-diyn-5-ol
• CAS: 503570-04-5
• 化学式: C₂₂H₄₀OSi
• 分子量: 348.644
• InChiKey: CLDBBRRTPGFOJJ-UHFFFAOYSA-N

物化性质

• 沸点：
  412.0±47.0 °C(Predicted)
• 密度：
  0.887±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.32
• 重原子数：
  24.0
• 可旋转键数：
  9.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  5-butyl-1-(triisopropylsilyl)nona-1,3-diyn-5-ol 在 四(三苯基膦)钯 、 copper(l) chloride 二异丙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 1,2-二氯乙烷 为溶剂， 反应 1.0h， 生成 5-butyl-1-(triisopropylsilyl)-3-[(triisopropylsilyl)ethynyl]nona-3,4-dien-1-yne
  参考文献：
  名称：

  1,3-Diethynylallenes: Carbon-Rich Modules for Three-Dimensional Acetylenic Scaffolding

  摘要：

  Regioselective Pd-0-catalyzed cross-coupling of substrates, which bear bispropargylic leaving groups with silyl-protected alkynes, has provided access to a variety of 1.3-diethynylailenes, a new family of modules for three-dimensional acetylenic scaffolding. In enantiomerically pure form, these C-rich building blocks could provide access - by oxidative oligomerization - to a fascinating new class of helical oligomers and polymers with all-carbon backbones (Fig. 2). In the first of two routes. a bispropargylic epoxide underwent ring opening during S(N)2'-type cross-coupling. and the resulting alkoxide was silyl-protected, providing 1,3-diethynylailenes (+/-)-8, (+/-)-12 (Scheme 3), and (+/-)-15 (Scheme 5). A more general approach involved bispropargylic carbonates or esters as substrates (Scheme 6-8), and this route was applied to the preparation of a series of 13-diethyrrylallenes to investigate how their overall stability against undesirable [2 + 2] cycloaddition is affected by the nature of the substituents at the allene moiety. The investigation showed that the 1,3-diethynylallene chromophore is stable against [2 + 2] cycloaddition only when protected by steric bulk and when additional relectron delocalization is avoided. The regioselectivity of the cross-coupling to the bispropargylic substrates is entirely controlled by steric factors: attack occurs at the alkyne moiety bearing the smaller substituent (Schemes 9 and 10). Oxidative Hay coupling of the terminally mono-deprotected 1.3-diethynylallene (+/-)-49 afforded the first dimer 50, probably as a mixture of two diastereoisomers (Scheme 12). Attempts to prepare a silyl-protected tetraethynylallene by the new methodology failed (Scheme 13). Control experiments (Schemes 14 - 16) showed that the Pd-0-catalyzed cross-coupling to butadiyne moieties in the synthesis of this still-elusive chromophore requires forcing conditions under which rapid [2 + 2] cycloaddition of the initial product cannot be avoided.

  DOI：

  10.1002/1522-2675(200210)85:10<3052::aid-hlca3052>3.0.co;2-4
• 作为产物：
  描述：

  5-壬酮 在 copper(l) chloride 正丙胺 、 盐酸羟胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 12.0h， 生成 5-butyl-1-(triisopropylsilyl)nona-1,3-diyn-5-ol
  参考文献：
  名称：

  1,3-Diethynylallenes: Carbon-Rich Modules for Three-Dimensional Acetylenic Scaffolding

  摘要：

  Regioselective Pd-0-catalyzed cross-coupling of substrates, which bear bispropargylic leaving groups with silyl-protected alkynes, has provided access to a variety of 1.3-diethynylailenes, a new family of modules for three-dimensional acetylenic scaffolding. In enantiomerically pure form, these C-rich building blocks could provide access - by oxidative oligomerization - to a fascinating new class of helical oligomers and polymers with all-carbon backbones (Fig. 2). In the first of two routes. a bispropargylic epoxide underwent ring opening during S(N)2'-type cross-coupling. and the resulting alkoxide was silyl-protected, providing 1,3-diethynylailenes (+/-)-8, (+/-)-12 (Scheme 3), and (+/-)-15 (Scheme 5). A more general approach involved bispropargylic carbonates or esters as substrates (Scheme 6-8), and this route was applied to the preparation of a series of 13-diethyrrylallenes to investigate how their overall stability against undesirable [2 + 2] cycloaddition is affected by the nature of the substituents at the allene moiety. The investigation showed that the 1,3-diethynylallene chromophore is stable against [2 + 2] cycloaddition only when protected by steric bulk and when additional relectron delocalization is avoided. The regioselectivity of the cross-coupling to the bispropargylic substrates is entirely controlled by steric factors: attack occurs at the alkyne moiety bearing the smaller substituent (Schemes 9 and 10). Oxidative Hay coupling of the terminally mono-deprotected 1.3-diethynylallene (+/-)-49 afforded the first dimer 50, probably as a mixture of two diastereoisomers (Scheme 12). Attempts to prepare a silyl-protected tetraethynylallene by the new methodology failed (Scheme 13). Control experiments (Schemes 14 - 16) showed that the Pd-0-catalyzed cross-coupling to butadiyne moieties in the synthesis of this still-elusive chromophore requires forcing conditions under which rapid [2 + 2] cycloaddition of the initial product cannot be avoided.

  DOI：

  10.1002/1522-2675(200210)85:10<3052::aid-hlca3052>3.0.co;2-4