(+/-)-6-[(tert-butyl)dimethylsilyloxy]-1-(trimethylsilyl)hexa-1,4-diyn-3-ol | 503569-80-0

• 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: (+/-)-6-[(tert-butyl)dimethylsilyloxy]-1-(trimethylsilyl)hexa-1,4-diyn-3-ol
• 英文别名: 6-(tert-butyldimethylsilanyloxy)-1-trimethylsilanylhexa-1,4-diyn-3-ol；6-[Tert-butyl(dimethyl)silyl]oxy-1-trimethylsilylhexa-1,4-diyn-3-ol；6-[tert-butyl(dimethyl)silyl]oxy-1-trimethylsilylhexa-1,4-diyn-3-ol
• CAS: 503569-80-0
• 化学式: C₁₅H₂₈O₂Si₂
• 分子量: 296.557
• InChiKey: CLWKULZLLAXPEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-6-[(tert-butyl)dimethylsilyloxy]-1-(trimethylsilyl)hexa-1,4-diyn-3-ol 在 barium permanganate 、 methyllithium lithium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 (+/-)-2-[2-({[(tert-butyl)dimethylsilyl]oxy}methyl)ethynyl]-2-[(trimethylsilyl)ethynyl]oxirane
  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：

  3-三甲基甲硅烷基丙炔醛 、 叔丁基二甲基(2-丙炔氧基)硅烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.17h， 以73%的产率得到(+/-)-6-[(tert-butyl)dimethylsilyloxy]-1-(trimethylsilyl)hexa-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

文献信息

• A Divergent Synthesis of Triyne Natural Products and Glycosylated Analogues Using a Carbenoid Rearrangement
  作者：Todd L. Lowary、Rik R. Tykwinski、Thanh Luu、Wei Shi

  DOI：10.1055/s-2005-918428

  日期：——

  Using a carbenoid rearrangement to introduce the conjugated acetylenic framework, a series of triynols has been synthesized in five steps from 1,4-butynediol. Several of the triyne alcohols are known natural products and others are glycosylated analogues. This route avoids the use of terminal diynes as precursors, which can be unstable and/or difficult to prepare. It is therefore procedurally attractive in comparison to more traditional routes such as the Cadiot-Chodkiewicz and Sonogashira coupling reactions.

  通过使用卡宾类重排引入共轭炔烃框架，已从1,4-丁炔二醇合成了一系列三炔醇，经过五个步骤。其中一些三炔醇是已知的天然产物，其他则是糖苷化类似物。这条路线避免了使用不稳定和/或难以制备的末端二炔作为前体。因此，与更传统的反应路线，如Cadiot-Chodkiewicz反应和Sonogashira偶联反应相比，这种方法在程序上更具吸引力。
• 1,3-Diethynylallenes: Carbon-Rich Modules for Three-Dimensional Acetylenic Scaffolding
  作者：Robert Livingston、Liam R. Cox、Severin Odermatt、François Diederich

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

  日期：2002.10

  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.