(+/-)-1-(triisopropylsilyl)non-1-yn-3-ol | 503569-86-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-1-(triisopropylsilyl)non-1-yn-3-ol
• CAS: 503569-86-6
• 化学式: C₁₈H₃₆OSi
• 分子量: 296.569
• InChiKey: UIHIZYNFODLBJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.54
• 重原子数：
  20.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  (+/-)-1-(triisopropylsilyl)non-1-yn-3-ol 在 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (+/-)-3-hexyl-1-(triisopropylsilyl)undeca-1,4-diyn-3-ol
  参考文献：
  名称：

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

  摘要：

  Regioselective Pd0 -catalyzed cross-coupling of bispropargylic precursors 1 with silyl-protected alkynes gave rise to the first 1,3-diethynylallenes 2 [Eq. (1), LG=leaving group]. In enantiomerically pure form, these novel carbon-rich modules could provide access-by oxidative oligomerization-to a fascinating new class of helical oligomers and polymers.

  DOI：

  10.1002/1521-3773(20010618)40:12<2334::aid-anie2334>3.0.co;2-7
• 作为产物：
  描述：

  在 双氧水 、 sodium hydroxide 作用下， 生成 (+/-)-1-(triisopropylsilyl)non-1-yn-3-ol
  参考文献：
  名称：

  镍催化未活化的α-烯烃与炔基亲电子试剂和B 2 pin 2的化学发散1，1-双官能化

  摘要：

  发散催化代表了增加分子复杂性和探索有机合成中催化方式的强大策略。在本文中，我们报道了未活化的α-烯烃的镍催化，化学发散的1,1-炔基硼化和1,1-二炔基化。这项研究不仅为炔丙基硼酸酯和宝石-二炔基烷烃的多样化合成提供了一种有效的模块化方案，而且还实现了Ni / B双金属中间体的可控，单或双交叉偶联。机理研究表明，乙硼试剂（B 2销2）在乙二酰化反应中起重要作用，既是还原剂又是瞬时辅助基团。值得注意的是，两种反应均显示出高区域选择性和良好的官能团耐受性。此外，产品的合成价值已通过几次下游转化得到证明。

  DOI：

  10.1021/acscatal.0c00898

文献信息

• 一种金属催化末端烯烃制备1,1-炔硼类化合 物的方法
  申请人：武汉大学

  公开号：CN111018899B

  公开（公告）日：2021-02-19

  本发明公开了一种金属催化末端烯烃制备1,1‑炔硼类化合物的方法。在金属镍类催化剂NiA、配体和碱的作用下，将联硼酸频哪醇酯，非活化的末端烯烃与三异丙基硅基乙炔溴溶于有机溶剂中并进行反应，得到结构的1,1‑炔硼类化合物。本发明方法可高效合成上述结构的1,1‑炔硼类化合物，具有优秀的区域选择性，并且产物中含有炔烃基团与硼基团，可应用于进一步转化，从而产生各种高度官能团化的化合物。
• 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.