1-(三甲基甲硅烷基)-2-戊炔-5-三甲基甲硅烷基醚 | 103620-63-9

• 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
• 中文名称: 1-(三甲基甲硅烷基)-2-戊炔-5-三甲基甲硅烷基醚
• 英文名称: 1-(Trimethylsilyl)-2-pentyn-5-trimethylsilyl ether
• 英文别名: 5-trimethylsilyl-1-trimethylsilyloxy-4-pentyne；trimethyl(5-(trimethylsilyl)pent-4-ynyloxy)silane；Trimethylsilyl 5-(trimethylsilyl)-4-pentynyl ether；trimethyl(5-trimethylsilyloxypent-1-ynyl)silane
• CAS: 103620-63-9
• 化学式: C₁₁H₂₄OSi₂
• 分子量: 228.482
• InChiKey: CHCWSBPYUGPTGD-UHFFFAOYSA-N

物化性质

• 沸点：
  222.4±23.0 °C(Predicted)
• 密度：
  0.842±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  5
• 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：

  1-(三甲基甲硅烷基)-2-戊炔-5-三甲基甲硅烷基醚 在 氢氧化钾 、 potassium carbonate 、 三乙胺 、 sodium iodide 作用下， 以 甲醇 、 水 、 丙酮 为溶剂， 反应 2.25h， 生成 1-Hex-5-ynyl-6,7-dimethoxy-3,4-dihydro-isoquinoline
  参考文献：
  名称：

  通过分子内亚氨酸甲酯亚甲基1,3-偶极环加成反应合成生物碱

  摘要：

  描述了神经毒性的毒扁豆碱生物碱d，1-塞孔的简明合成，其依赖于分子内环加成反应，该反应涉及“未稳定的”亚氨酸酯亚甲基和未活化的烯烃。通过偶合和偶极亲和体在芳基核上的邻位排列加强的刚性排列，增强了这种环化的便利性。在尝试合成赤藓骨架的过程中揭示了这种环形方法的合成局限性。在这种情况下，亚胺酸酯亚甲基的质子性重排为异构烯胺，从而排除了所需的环化反应。

  DOI：

  10.1016/s0040-4020(01)96709-2
• 作为产物：
  描述：

  5-(三甲基硅烷基)-4-戊炔-1-醇 反应 24.0h， 生成 2-methyleneoxolane 、 1-(三甲基甲硅烷基)-2-戊炔-5-三甲基甲硅烷基醚
  参考文献：
  名称：

  Alkaline Earth Catalysis of Alkynyl Alcohol Hydroalkoxylation/Cyclization

  摘要：

  Heavier alkaline earth bis(trimethylsilyl)amides [Ae{N(SiMe3)(2)}(2)](2) (Ae = Ca, Sr, Ba) are shown to act as effective precatalysts for the regioselective intramolecular hydroalkoxylation/cyclization of a wide range of alkynyl and allenyl alcohols. In the majority of cases, cyclization of alkynyl alcohols produces mixtures of the possible endo- and exocyclic enol ether products, rationalized as a consequence of alkynylalkoxide isomerization to the corresponding allene derivatives. Cyclization rates for terminal alkynyl alcohols were found to be significantly higher than for substrates bearing internal alkynyl substituents, while the efficacy of cyclization was in general found to be determined by a combination of stereoelectronic influences and the thermochemical viability of the specific alkaline earth metal catalysis, which we suggest is determined by the individual M-O bond strengths. Kinetic studies have provided a rate law pertaining to a pronounced catalyst inhibition with increasing [substrate], indicating that turnover-limiting insertion of C-C unsaturation into the M-O bond requires the dissociation of substrate molecules away from the Lewis acidic alkaline earth center.

  DOI：

  10.1021/om3008663

文献信息

• Intramolecular Heck Couplings and Cycloisomerizations of Bromodienes and Enynes with 1′,1′-Disubstituted Methylenecyclopropane Terminators: Efficient Syntheses of [3]Dendralenes
  作者：Stefan Bräse、Hanno Wertal nee Nüske、Daniel Frank、Denis Vidović、Armin de Meijere

  DOI：10.1002/ejoc.200500330

  日期：2005.10

  atom-economic, palladium-catalyzed cycloisomerization. The vinylpalladium halide intermediate generated by initial carbopalladation of the 1,6-enyne 10-H with in situ generated phenylpalladium iodide also underwent the same cyclization cascade to yield the correspondingly phenyl-substituted cyclic [3]dendralene 41-Ph (21 %). The palladium-catalyzed cycloisomerization of the alk-1-ene-7,12-diyne 33-H gave the

  具有四取代亚甲基环丙烷端基的 2-Bromoalka-1,n-二烯如 9、30 和 14（n = 7），在钯催化下，经过环丙烷开环环化得到 2-乙烯基-3-亚甲基-1-环烯烃 41 (n = 6)、42 (n = 7) 和 43，它们分别是取代的单环 [3] 树枝烯，产率分别为 65%、63% 和 70%。通过更原子经济的方法从相应的 1,6- (10-H, 15) 和 1,7-烯炔 (28-H) 中分离出相同的交叉共轭三烯，收率良好（77-92%） , 钯催化的环异构化。通过 1,6-烯炔 10-H 与原位生成的苯基碘化钯的初始碳钯化生成的乙烯基卤化钯中间体也经历了相同的环化级联反应，生成相应的苯基取代的环状 [3] 树枝状化合物 41-Ph (21 %)。1-烯-7,12-二炔 33-H 的钯催化环异构化得到双环交叉共轭四烯 50-H (43%)。使用专门设计的模型系统 20-H 证明
• Carbocyclic ring expansion reactions via free radical pathways - part III
  作者：Jack E. Baldwin、Robert M. Adlington、Rajinder Singh

  DOI：10.1016/0040-4020(92)85014-6

  日期：1992.1

  The free radical ring expansion methodology recently described1, leading to the formation of medium sized ring ketones from cyclohexanone precursors has been applied to different side chains and ring sizes. In addition precursors based on lactone rings have been prepared and subjected to radical forming reaction conditions.

  最近描述的自由基环膨胀方法1导致从环己酮前体形成中等大小的环酮已应用于不同的侧链和环大小。另外，已经制备了基于内酯环的前体，并使其经受自由基形成反应条件。
• A selective method for oxygen deprotection in bistrimethylsilylated terminal alkynols
  作者：Richard A. Bunce、Donald V. Hertzler

  DOI：10.1021/jo00368a008

  日期：1986.9
• Seo, SungYong; Yu, Xianghua; Marks, Tobin J., Journal of the American Chemical Society, 2009, vol. 131, p. 263 - 276
  作者：Seo, SungYong、Yu, Xianghua、Marks, Tobin J.

  DOI：——

  日期：——
• Alkaline Earth Catalysis of Alkynyl Alcohol Hydroalkoxylation/Cyclization
  作者：Christine Brinkmann、Anthony G. M. Barrett、Michael S. Hill、Panayiotis A. Procopiou、Stephanie Reid

  DOI：10.1021/om3008663

  日期：2012.10.22

  Heavier alkaline earth bis(trimethylsilyl)amides [AeN(SiMe3)(2)}(2)](2) (Ae = Ca, Sr, Ba) are shown to act as effective precatalysts for the regioselective intramolecular hydroalkoxylation/cyclization of a wide range of alkynyl and allenyl alcohols. In the majority of cases, cyclization of alkynyl alcohols produces mixtures of the possible endo- and exocyclic enol ether products, rationalized as a consequence of alkynylalkoxide isomerization to the corresponding allene derivatives. Cyclization rates for terminal alkynyl alcohols were found to be significantly higher than for substrates bearing internal alkynyl substituents, while the efficacy of cyclization was in general found to be determined by a combination of stereoelectronic influences and the thermochemical viability of the specific alkaline earth metal catalysis, which we suggest is determined by the individual M-O bond strengths. Kinetic studies have provided a rate law pertaining to a pronounced catalyst inhibition with increasing [substrate], indicating that turnover-limiting insertion of C-C unsaturation into the M-O bond requires the dissociation of substrate molecules away from the Lewis acidic alkaline earth center.