2-methyl-6-trimethylsilyl-3,5-hexadiyn-2-ol | 4257-10-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-6-trimethylsilyl-3,5-hexadiyn-2-ol
• 英文别名: 1-(Trimethylsilyl)-5-methylhexa-1,3-diyn-5-ol；2-methyl-6-trimethylsilylhexa-3,5-diyne-2-ol；2-methyl-6-(trimethylsilyl)hexa-3,5-diyn-2-ol；1-Trimethylsilyl-5-methyl-hexadiin-(1,3)-ol-(5)；Trimethylsilyl-<5-hydroxy-2-methyl-hexadiin-(1,3)-yl>-silan；1-Trimethylsilyl-2-methyl-hexa-3,5-diin-2-ol；6-Trimethylsilyl-2-methylhexa-3,5-diyn-2-ol；2-methyl-6-trimethylsilylhexa-3,5-diyn-2-ol
• CAS: 4257-10-7
• 化学式: C₁₀H₁₆OSi
• 分子量: 180.322
• InChiKey: NCPIEYUZNMOEIQ-UHFFFAOYSA-N

物化性质

• 熔点：
  67 °C
• 沸点：
  85 °C(Press: 3 Torr)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.64
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-6-trimethylsilyl-3,5-hexadiyn-2-ol 在 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 2-methyl-3,5-hexadiyn-2-ol
  参考文献：
  名称：

  Regio- and stereoselectivity in the concatenated enyne cross metathesis–metallotropic [1,3]-shift of terminal 1,3-diyne

  摘要：

  Enyne cross metathesis of terminal 1,3-diynes with various alkenes afforded two products of distinctive connectivity, as the result of a uniform mode of initiation but different modes of termination events with or without metallotropic [1,3]-shift. Steric and electronic factors of the substituents on the 1,3-diynes play an important role in controlling the metallotropic [1,3]-shift of the propagating allcylidene intermediates and their regioselective trapping to the final products. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.08.024
• 作为产物：
  描述：

  三甲基乙炔基硅 在 palladium diacetate 、 trisodium tris(3-sulfophenyl)phosphine N-碘代丁二酰亚胺 、 silver nitrate 、 三乙胺 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 2.5h， 生成 2-methyl-6-trimethylsilyl-3,5-hexadiyn-2-ol
  参考文献：
  名称：

  New synthetic applications of water-soluble acetate Pd/TPPTS catalyst generated in Situ. evidence for a true Pd(0) species intermediate

  摘要：

  Studies on the sp-sp intermolecular coupling reactions with the palladium water-soluble catalyst prepared in situ from palladium(II) acetate and sulfonated triphenylphosphine P(C6H4-m-SO3Na)(3) (TPPTS) in a homogeneous acetonitrile-water system, without Cu(I) promotor, afford diynes with moderate yields (45-65%). Under the same conditions, the sp(2)-sp coupling of 2-iodophenols or 2-iodoanilines and terminal alkynes followed by intramolecular cyclization gives indolic and furanic products in good yields (60-99%). Under these aqueous conditions, an efficient and short synthesis of eutypine illustrated the synthetic potentiality of the coupling. Furthermore, through a series of kinetic and P-31 NMR experiments, we have demonstrated that a mixture of Pd(OAc)(2) and TPPTS affords spontaneously a palladium(0) complex, through formation of bivalent complex Pd(OAc)(2)-(TPPTS)(2). A detailed mechanism of the reaction has been investigated thoroughly and the pertinent rate constants measured. The resulting palladium(0) complex reacts with phenyl iodide via an oxidative addition. This complex is considerably less reactive than the corresponding complex generated from PPh(3), probably due to steric effects.

  DOI：

  10.1021/jo00126a037

文献信息

• Interligand Interactions Dictate the Regioselectivity of<i>trans</i>-Hydrometalations and Related Reactions Catalyzed by [Cp*RuCl]. Hydrogen Bonding to a Chloride Ligand as a Steering Principle in Catalysis
  作者：Stephan M. Rummelt、Karin Radkowski、Dragoş-Adrian Roşca、Alois Fürstner

  DOI：10.1021/jacs.5b01475

  日期：2015.4.29

  mode in the presence of [Cp*Ru(MeCN)3]PF6 (1) as the catalyst; however, the regioselectivity is often poor with unsymmetrical substrates. This problem can be solved upon switching to a catalyst comprising a [Ru-Cl] bond, provided that the acetylene derivative carries a protic functional group. The R3M unit is then delivered with high selectivity to the alkyne-C atom proximal to this steering substituent

  在 [Cp*Ru(MeCN)3]PF6 (1) 作为催化剂的存在下，内炔与 R3M-H（M = Si、Ge、Sn）的反应遵循非常规的反式加成模式；然而，不对称底物的区域选择性通常很差。如果乙炔衍生物带有质子官能团，则该问题可以通过改用包含 [Ru-Cl] 键的催化剂来解决。然后，R3M 单元以高选择性传递到该控制取代基附近的炔烃-C 原子。这种导向效应源于极化的 [Ru-Cl] 键与质子取代基进行氢键合的能力，这有助于将炔烃上传、激活和锁定在配位球内。氯化物与 -MR3 中心的额外配位体接触将进入的试剂定位在匹配的方向，从而转化为高区域选择性。所提出的负载催化剂内的二次相互作用与大量制备和光谱数据以及固态新型钌 π 配合物 10 和 11 的结构一致。此外，还提出了 [Ru(σ-锡烷)] 配合物 (12a) 的第一个 X 射线结构，它确实具有外围 Ru-Cl……MR3 接触；该加合物也证实炔烃反式加成化学可能涉及
• An Efficient Heterogeneous Palladium(0)-Catalysed Cross-Coupling between 1-Bromoalkynes and Terminal Alkynes Leading to Unsymmetrical 1,3-Diynes
  作者：Zhaotao Xu、Jinting Ai、Mingzhong Cai

  DOI：10.3184/174751918x15208574638459

  日期：2018.3

  efficient heterogeneous palladium(0)-catalysed cross-coupling of 1-bromoalkynes with terminal alkynes was achieved in DMF at room temperature in the presence of 5 mol% of MCM-41-immobilised bidentate phosphine palladium(0) complex [MCM-41-2P-Pd(0)] and 2 mol% of CuI with Et3N as base, yielding a variety of unsymmetrical 1,3-diynes in moderate to good yields. This heterogeneous palladium(0) complex

  在 5 mol% 的 MCM-41 固定化双齿膦钯 (0) 络合物 [MCM-41] 存在下，室温下在 DMF 中实现了 1-溴炔烃与末端炔烃的高效异相钯 (0) 催化交叉偶联-2P-Pd(0)] 和 2 mol% 的 CuI，以 Et3N 为碱，以中等至良好的产率产生各种不对称的 1,3-二炔。这种异质钯 (0) 络合物可以通过反应溶液的简单过滤轻松回收，并至少循环 7 次而不会显着降低活性。
• Tuning of cross-Glaser products mediated by substrate–catalyst polymeric backbone interactions
  作者：Sharanjeet Kaur、Aritra Mukhopadhyaya、Abdul Selim、Vijayendran Gowri、K. M. Neethu、Arif Hassan Dar、Shaifali Sartaliya、Md. Ehesan Ali、Govindasamy Jayamurugan

  DOI：10.1039/c9cc08565c

  日期：——

  Tuneable selectivity in cross-Glaser products is achieved by tweaking the catalyst-backbone. The interaction responsible for this is unravelled.

  通过调整催化剂骨架实现了交叉格拉瑟产物中的可调选择性。负责这一作用的相互作用被揭示。
• Ruthenium-Catalyzed Alkyne<i>trans</i>-Hydrometalation: Mechanistic Insights and Preparative Implications
  作者：Dragoş-Adrian Roşca、Karin Radkowski、Larry M. Wolf、Minal Wagh、Richard Goddard、Walter Thiel、Alois Fürstner

  DOI：10.1021/jacs.6b12517

  日期：2017.2.15

  [Cp*RuCl]4 (1) has previously been shown to be the precatalyst of choice for stereochemically unorthodox trans-hydrometalations of internal alkynes. Experimental and computational data now prove that the alkyne primarily acts as a four-electron donor ligand to the catalytically active metal fragment [Cp*RuCl] but switches to adopt a two-electron donor character once the reagent R3MH (M = Si, Ge, Sn)

  [Cp*RuCl]4 (1) 先前已被证明是内部炔烃的立体化学非正统反式氢金属化的首选预催化剂。实验和计算数据现在证明，炔主要作为催化活性金属片段 [Cp*RuCl] 的四电子供体配体，但一旦试剂 R3MH（M = Si、Ge、 Sn) 进入配体球。在立体确定步骤中，由此产生的负载复合物通过内球机制演变成钌环丙烯，并迅速转化为产物。与低计算势垒一致，光谱和制备数据表明，该反应不仅是可能的，而且有时在低温下甚至是有利的。重要的，当使用在三键附近带有 -OH 或 -NHR 基团的不对称炔烃时，这种反式氢金属化的特点是具有出色的区域选择性。质子取代基和极化 [Ru-Cl] 单元之间的新生氢桥将方向性强加到相关中间体的配体球上，最终解释了 R3M- 基团选择性传递到靠近转向的乙炔 C 原子取代基。配体间氢键还允许在多不饱和化合物的反应中利用位点选择性，因为炔丙基底物比普通炔烃结合得更紧密；即使是共轭
• [EN] PROCESS FOR THE RUTHENIUM CATALYZED TRANS-SELECTIVE HYDROSTANNATION OF ALKYNES<br/>[FR] PROCÉDÉ D'HYDROSTANNATION TRANS-SÉLECTIVE D'ALCYNES PAR CATALYSE AU RUTHÉNIUM
  申请人：STUDIENGESELLSCHAFT KOHLE MBH

  公开号：WO2015059006A1

  公开（公告）日：2015-04-30

  The present invention refers to a process for the ruthenium-catalyzed trans-selective hydrostannation of alkynes and the so-obtained products. The inventive process makes use of a tin hydride which is reacted with an alkyne in the presence of a cyclopentadienyl-coordinated ruthenium catalyst.

  本发明涉及一种钌催化的烯烃选择性水锡化反应的方法以及所得到的产物。该创新方法利用一种锡氢化合物与烯烃在环戊二烯基配位的钌催化剂存在下发生反应。