(1-(tert-butyldimethylsilanyloxy)methyl)-2-trimethylsilanylethynylbenzene | 169123-87-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1-(tert-butyldimethylsilanyloxy)methyl)-2-trimethylsilanylethynylbenzene
• 英文别名: tert-butyldimethyl{2-[(trimethylsilyl)ethynyl]benzyloxy}silane；Tert-butyl-dimethyl-[[2-(2-trimethylsilylethynyl)phenyl]methoxy]silane
• CAS: 169123-87-9
• 化学式: C₁₈H₃₀OSi₂
• 分子量: 318.607
• InChiKey: ILXKTXNKESGVLW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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-(tert-butyldimethylsilanyloxy)methyl)-2-trimethylsilanylethynylbenzene 在 甲醇 、 sodium sulfide 作用下， 反应 0.17h， 以90%的产率得到tert-butyl((2-ethynylbenzyl)oxy)dimethylsilane
  参考文献：
  名称：

  Sodium sulfide in methanol: a two-in-one reagent for deprotection of silyl and formation of propargyl sulfide

  摘要：

  A new reagent Na2S/MeOH for silyl deprotection has been developed. The reagent has several advantages which include deprotection of C-TMS, O-TMS, O-TBS, and O-TBDPS, selective removal of C-TMS and O-TMS in the presence of O-TBS and simultaneous desilylation and sulfide formation in one pot. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.04.104
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 {2-[2-(trimethylsilyl)ethynyl]phenyl}methanol 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以92%的产率得到(1-(tert-butyldimethylsilanyloxy)methyl)-2-trimethylsilanylethynylbenzene
  参考文献：
  名称：

  Platinum and Ruthenium Chloride-Catalyzed Cycloisomerization of 1-Alkyl-2-ethynylbenzenes: Interception of π-Activated Alkynes with a Benzylic C−H Bond

  摘要：

  Air-stable and commercially available alkynophilic metal salts, such as PtCl2, PtCl4, and [RuCl2(CO)(3)](2), catalyze the cycloisomerization of 1-alkyl-2-ethynylbenzenes to produce Substituted indenes even at all ambient temperature. Electrophilically activated alkynes can be intercepted by simple benzylic C-H bonds at primary, secondary, and tertiary carbon centers. Mechanistic studies, such as labeling studies and kinetic isotope and substituent effects, indicate that the cycloisomerization proceeds through the formation of a vinylidene intermediate and turnover-limiting 1,5-shift of benzylic hydrogen.

  DOI：

  10.1021/jo901045g

文献信息

• Convergent synthesis of pyrrolidines, piperidines, perhydroazepines and tetrahydroisoquinolines via zirconocene η2-imine complexes
  作者：Michael C.J. Harris、Richard J. Whitby、Julian Blagg

  DOI：10.1016/0040-4039(95)00741-t

  日期：1995.6

  Zirconocene η2-imine complexes formed by a CH activation route from a variety of amines are trapped by ω-halo-alkenes or -alkynes to afford 2,3-disubstituited pyrrolidines, piperidines and perhydroazepines on work up and cyclisation. In some cases it was necessary to use a protected hydroxyl group rather than the halide and cyclise in a separate step through selective formation of the O-mesylate.

  锆η 2层由CH活化途径由不同的胺形成亚胺的复合物由ω卤代烯烃被捕获或-alkynes，得到2,3- disubstituited吡咯烷，哌啶和perhydroazepines上的后处理和环化。在某些情况下，有必要在一个单独的步骤中通过选择性形成O-甲磺酸酯来使用受保护的羟基，而不是卤化物和环化。
• Sodium sulfide in methanol: a two-in-one reagent for deprotection of silyl and formation of propargyl sulfide
  作者：Ishita Hatial、Raja Mukherjee、Kalyan Senapati、Amit Basak

  DOI：10.1016/j.tetlet.2015.04.104

  日期：2015.7

  A new reagent Na2S/MeOH for silyl deprotection has been developed. The reagent has several advantages which include deprotection of C-TMS, O-TMS, O-TBS, and O-TBDPS, selective removal of C-TMS and O-TMS in the presence of O-TBS and simultaneous desilylation and sulfide formation in one pot. (c) 2015 Elsevier Ltd. All rights reserved.
• Platinum and Ruthenium Chloride-Catalyzed Cycloisomerization of 1-Alkyl-2-ethynylbenzenes: Interception of π-Activated Alkynes with a Benzylic C−H Bond
  作者：Mamoru Tobisu、Hiromi Nakai、Naoto Chatani

  DOI：10.1021/jo901045g

  日期：2009.8.7

  Air-stable and commercially available alkynophilic metal salts, such as PtCl2, PtCl4, and [RuCl2(CO)(3)](2), catalyze the cycloisomerization of 1-alkyl-2-ethynylbenzenes to produce Substituted indenes even at all ambient temperature. Electrophilically activated alkynes can be intercepted by simple benzylic C-H bonds at primary, secondary, and tertiary carbon centers. Mechanistic studies, such as labeling studies and kinetic isotope and substituent effects, indicate that the cycloisomerization proceeds through the formation of a vinylidene intermediate and turnover-limiting 1,5-shift of benzylic hydrogen.