(+/-)-3-(tert-butyl)-6,6-dimethyl-1-(trimethylsilyl)hepta-1,4-diyn-3-ol | 503569-94-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-3-(tert-butyl)-6,6-dimethyl-1-(trimethylsilyl)hepta-1,4-diyn-3-ol
• CAS: 503569-94-6
• 化学式: C₁₆H₂₈OSi
• 分子量: 264.483
• InChiKey: XJUBSZPMFJNKLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (+/-)-3-(tert-butyl)-6,6-dimethyl-1-(trimethylsilyl)hepta-1,4-diyn-3-ol 在 4-二甲氨基吡啶 、 sodium hydroxide 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 27.0h， 生成 (3S)-3-(tert-butyl)-6,6-dimethylhepta-1,4-diyn-3-ol
  参考文献：
  名称：

  1,3-二乙炔基丙二烯：稳定单体、长度限定的低聚物、不对称合成和光学分辨率

  摘要：

  已经合成了一系列不同取代的 1,3-二乙炔基丙二烯 (DEA)，证实了先前引入的构建协议可以容忍各种功能组。新的 DEA 带有至少一个极性基团，以促进手性固定相上的对映异构体分离并允许进一步功能化。它们是热和环境稳定的化合物，因为靠近枯草烯部分的大取代基抑制了发生 [2+2] 环二聚化的趋势。通过在 Glaser-Hay 条件下氧化偶联单体 DEA，获得了一系列长度限定的低聚物作为立体异构体的混合物。电子吸收数据表明，由于丙二烯 π 系统的正交性，在低聚主链上缺乏扩展的 π 电子共轭。值得注意的是，即使立体异构体的复杂混合物也只产生一组单一的 NMR 信号，这突显了无环烯丙炔结构中的低立体分化。DEA 的光学分辨率是一个惊人的挑战，并报告了分析水平的初步结果。通过 Pd 介导的 SN2' 型炔烃与光学纯双炔前体的交叉偶联的不对称合成开辟了另一条有希望的路线，以制备立体选择性目前高达 78%

  DOI：

  10.1002/ejoc.200700373
• 作为产物：
  描述：

  3,3-二甲基-1-丁炔 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.75h， 生成 (+/-)-3-(tert-butyl)-6,6-dimethyl-1-(trimethylsilyl)hepta-1,4-diyn-3-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