2-methyl-2-<(triethylsilyl)oxy>-3-butyne | 17963-41-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-<(triethylsilyl)oxy>-3-butyne
• 英文别名: [(1,1-dimethylprop-2-ynyl)oxy](triethyl)silane；triethyl((2-methylbut-3-yn-2-yl)oxy)silane；2-methyl-2-(triethylsilyl)oxy-3-butyne；triethyl-(1,1-dimethyl-prop-2-ynyloxy)-silane；Triaethyl-(1,1-dimethyl-prop-2-inyloxy)-silan；[(1,1-dimethyl-2-propynyl)oxy]triethylsilane；Triethyl[(2-methylbut-3-yn-2-yl)oxy]silane；triethyl(2-methylbut-3-yn-2-yloxy)silane
• CAS: 17963-41-6
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: CAAPVQVUCVXKKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-2-<(triethylsilyl)oxy>-3-butyne 在 palladium on activated charcoal 四(三苯基膦)钯 、 正丁基锂 、 四丁基氟化铵 、 氢气 、 氧气 、 焦磷酸硫胺素 、 三苯基膦 、 zinc(II) chloride 作用下， 以 甲醇 为溶剂， 反应 9.17h， 生成 (4Z)-5-isopropyl-2,6-dimethyl-3-heptene-2,5,6-triol
  参考文献：
  名称：

  Photosensitized Oxygenation of Twisted 1,3-Dienes:  Abnormally Higher Reactivity of Vinyl Hydrogen Rather than Allyl Hydrogen toward Singlet Oxygen

  摘要：

  As one of the novel examples to investigate the characteristic reactivity of significantly twisted 1,3-dienes, the photosensitized oxygenation of two types of significantly twisted 1,3-dienes, cis-beta-ionol derivative 2 and acyclic derivative Il, is investigated. Photosensitized oxygenation of 2a-f and 11a-e revealed that the vinyl hydrogen Ha was more reactive than the allyl hydrogen Hb. Thus, phenyl derivative 2e and tert-butyl-substituted compound lid selectively produced allenes 3e and 13d in 67% and 75% yield resulting from the ene reaction of the vinyl hydrogen Ha rather than allyl alcohols 4e and 14d resulting from the allyl hydrogen abstraction in 24% and 8% yield, respectively. Furthermore, in the case of methyl-substituted compound 11b, the extent of the inherent reactivity of the vinyl hydrogen Ha was similar to that of the allyl hydrogen He. On the basis of X-ray analysis and NIM and MO calculations, the discovered abnormally higher reactivity of the vinyl hydrogen would be rationalized by considering mainly the large sigma*-pi orbital interaction between the vinyl C-H bond and another double bond in significantly twisted 1,3-dienes resulting from calculations of HOMO electron densities.

  DOI：

  10.1021/jo980955o
• 作为产物：
  描述：

  三乙基氯硅烷 、 2-甲基-3-丁炔-2-醇 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以100%的产率得到2-methyl-2-<(triethylsilyl)oxy>-3-butyne
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044

文献信息

• Half-Sandwich Ruthenium Carbene Complexes Link<i>trans</i>-Hydrogenation and<i>gem</i>-Hydrogenation of Internal Alkynes
  作者：Alexandre Guthertz、Markus Leutzsch、Lawrence M. Wolf、Puneet Gupta、Stephan M. Rummelt、Richard Goddard、Christophe Farès、Walter Thiel、Alois Fürstner

  DOI：10.1021/jacs.8b00665

  日期：2018.2.28

  E-alkenes are formed by trans-delivery of the two H atoms of H2. A combined experimental and computational study now provides a comprehensive mechanistic picture: a metallacyclopropene (η2-vinyl complex) is primarily formed, which either evolves into the E-alkene via a concerted process or reacts to give a half-sandwich ruthenium carbene; in this case, one of the C atoms of the starting alkyne is converted

  用 [Cp*Ru] 基催化剂对内部炔烃进行氢化的特点是非正统的立体化学过程，因为 E-烯烃是通过 H2 的两个 H 原子的反式传递形成的。一项结合实验和计算的研究现在提供了一个全面的机理图：主要形成金属环丙烯（η2-乙烯基配合物），它要么通过协同过程演变成 E-烯烃，要么反应生成半夹心钌卡宾；在这种情况下，起始炔烃的一个碳原子被转化为亚甲基。这种转变代表了 π 键的正式宝石氢化，这几乎没有任何先例。反式氢化和宝石氢化的障碍相似：而 DFT 预测偏向于反式氢化，而 CCSD(T) 发现宝石氢化稍微容易一些。卡宾一旦形成，将结合第二个 H2 分子并演变成所需的 E-烯烃、位置烯烃异构体或相应的烷烃；这种缔合途径解释了为什么双键异构化和过度还原与反式氢化竞争。计算的场景与副氢诱导极化转移 (PHIP) NMR 数据一致，该数据证实了 H2 的直接传递、通过 gem-氢化形成卡宾中间体，以及它们向
• Cobalt-Catalyzed Cross-Couplings of Bench-Stable Alkynylzinc Pivalates with (Hetero)Aryl and Alkenyl Halides
  作者：Jeffrey M. Hammann、Lucie Thomas、Yi-Hung Chen、Diana Haas、Paul Knochel

  DOI：10.1021/acs.orglett.7b01722

  日期：2017.7.21

  A catalytic system consisting of CoCl2·2LiCl and TMEDA enables the cross-coupling of various electron-poor aryl and heteroaryl halides with various alkynylzinc pivalates. Coupling with alkenyl halides proceeds with retention of configuration.

  由CoCl 2 ·2LiCl和TMEDA组成的催化体系使各种贫电子的芳基卤化物和杂芳基卤化物与各种炔基新戊酸酯发生交叉偶联。与烯基卤化物的偶联继续保持构型。
• Organocatalytic Synthesis of Highly Substituted Furfuryl Alcohols and Amines
  作者：J. Stephen Clark、Alistair Boyer、Anthony Aimon、Paloma Engel García、David M. Lindsay、Andrew D. F. Symington、Yves Danoy

  DOI：10.1002/anie.201207300

  日期：2012.11.26

  Top cat! Tetrahydrothiophene is an efficient organocatalyst for the synthesis of highly substituted furfuryl products from readily accessible electron‐poor enynes under neutral reaction conditions. This process is applicable to a wide range of nucleophiles and enynes and can be used in a domino organocatalysis sequence.

  顶级猫！四氢噻吩是一种有效的有机催化剂，可在中性反应条件下从易获得的电子贫乏的炔烃中合成高度取代的糠基产物。该方法适用于广泛的亲核试剂和烯炔，并且可以用于多米诺有机催化序列中。
• Hydrogenative Cyclopropanation and Hydrogenative Metathesis
  作者：Sebastian Peil、Alexandre Guthertz、Tobias Biberger、Alois Fürstner

  DOI：10.1002/anie.201904256

  日期：2019.6.24

  The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution

  以[Cp X RuCl]为催化剂的炔丙醇衍生物的非常规双氢加氢，首先需要形成钢琴凳形碳烯钌。这些反应性中间体可以通过形式化的复分解事件与链状烯烃截获，生成环丙烷或环状烯烃。反应过程主要取决于烯烃捕集器的取代方式。
• Hydrogenative Metathesis of Enynes via Piano-Stool Ruthenium Carbene Complexes Formed by Alkyne <i>gem</i>-Hydrogenation
  作者：Sebastian Peil、Giovanni Bistoni、Richard Goddard、Alois Fürstner

  DOI：10.1021/jacs.0c07808

  日期：2020.10.28

  discovered gem-hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp*RuCl]4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis

  最近唯一发现的内部炔烃的宝石氢化是一种全新的转化，其中二氢的两个 H 原子都转移到三键的同一个 C 原子上，而另一个位置转化为离散的金属卡宾配合物。[Cp*RuCl]4 是目前选择的催化剂：所得的钢琴凳式钌卡宾可以与系链烯烃结合进入环丙烷化或复分解，并且这种反应性中间体的典型例子与连接到钌中心的烯烃通过 X 射线衍射分离和表征。烯烃的取代模式决定了是否发生复分解或环丙烷化：使用性质大不相同的烯烃进行系统调查，并结合局部耦合簇理论水平的机理计算研究，可以对制备结果进行分类，并提出具有预测能力的直观模型。如果发生复分解，该模型将反应过程与双键的极化以及形成的二级卡宾配合物的稳定性联系起来。“氢化复分解”首次应用于 sinularones E 和 F 的全合成与这种解释一致，并允许这些海洋天然产物的拟议结构得到证实。在此合成过程中，发现宝石氢化也为 C-H 功能化提供了机会。而且，甲硅烷基化炔烃