(3-cyclohexylprop-1-ynyl)trimethylsilane | 132539-51-6

• 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
• 英文名称: (3-cyclohexylprop-1-ynyl)trimethylsilane
• 英文别名: 3-Cyclohexylprop-1-ynyl(trimethyl)silane
• CAS: 132539-51-6
• 化学式: C₁₂H₂₂Si
• 分子量: 194.392
• InChiKey: WISOZSGMZQLNCY-UHFFFAOYSA-N

物化性质

• 沸点：
  224.7±9.0 °C(Predicted)
• 密度：
  0.848±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (3-cyclohexylprop-1-ynyl)trimethylsilane 在 三氟化硼乙醚 、 二异丁基氢化铝 作用下， 反应 21.5h， 生成 methyl (Z)-2-(trimethylsilyl)-4-cyclohexyl-2-butenoate
  参考文献：
  名称：

  (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals

  摘要：

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.

  DOI：

  10.1021/jo00007a039
• 作为产物：
  描述：

  3-环己基-1-丙炔 、 三甲基硅烷基二乙胺 在 zinc(II) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.25h， 生成 (3-cyclohexylprop-1-ynyl)trimethylsilane
  参考文献：
  名称：

  通过糖基支架的环收缩探索骨骼多样性。

  摘要：

  芳基醚C-糖苷支架已由C-糖基化，然后由Pd（0）介导的苯酚进行烯丙基取代，由三-O-乙酰基-D-葡糖醛制备。使芳基醚经历[3,3]-σ重排以产生3-吡喃基-酚或Au（III）介导的环收缩以产生高度取代的四氢呋喃。[结构：见文字]

  DOI：

  10.1021/ol0618252

文献信息

• C(sp)–C(sp³) Bond Formation through Cu-Catalyzed Cross-Coupling of<i>N</i>-Tosylhydrazones and Trialkylsilylethynes
  作者：Fei Ye、Xiaoshen Ma、Qing Xiao、Huan Li、Yan Zhang、Jianbo Wang

  DOI：10.1021/ja3004792

  日期：2012.4.4

  Copper-catalyzed cross-coupling of N-tosylhydrazones with trialkylsilylethynes leads to the formation of C(sp)-C(sp(3)) bonds. Cu carbene migratory insertion is proposed to play the key role in this transformation.

  N-甲苯磺酰腙与三烷基甲硅烷基乙炔的铜催化交叉偶联导致形成 C(sp)-C(sp(3)) 键。提出Cu卡宾迁移插入在这种转变中起关键作用。
• Mild propargylic oxidation using a diacetoxyiodobenzene/tert-butyl hydroperoxide protocol
  作者：Yi Zhao、Angela Wan Ting Ng、Ying-Yeung Yeung

  DOI：10.1016/j.tetlet.2014.06.032

  日期：2014.7

  A mild propargylic oxidation of alkynes is reported using a diacetoxyiodobenzene/tert-butyl hydroperoxide (DIB/TBHP) protocol. The reactions proceed smoothly at 0 °C and a number of α,β-unsaturated alkynoic ketones are obtained.

  据报道，使用二乙酰氧基碘苯/氢过氧化叔丁基（DIB / TBHP）方案可进行炔烃的轻度炔丙基氧化。反应在0°C下平稳进行，获得了许多α，β-不饱和炔烃酮。
• Propargylic Silanes: Convenient Syntheses of 1-Trimethylsilyl-2-alkynes, 1,3-Bis[trimethylsilyl]-1-alkynes, and 3-Trimethylsilyl-1-alkynes
  作者：Shyamala Rajagopalan、George Zweifel

  DOI：10.1055/s-1984-30741

  日期：——
• Fleming, Ian; Morgan, Ian T.; Sarkar, Achintya K., Journal of the Chemical Society. Perkin transactions I, 1998, # 17, p. 2749 - 2763
  作者：Fleming, Ian、Morgan, Ian T.、Sarkar, Achintya K.

  DOI：——

  日期：——
• Reversilbility of titanocene-catalyzed hydromagnesation of silylacetylenes
  作者：Marina A. Djadchenko、Kasimir K. Pivnitsky、Jorg Spanig、Hans Schick

  DOI：10.1016/0022-328x(91)86189-w

  日期：1991.1

  The regioisomeric silylvinylmagnesium compounds A and B, products of titanocene-catalyzed hydromagnesation of trimethylsilylacetylenes, are in a rapid dynamic equilibrium with starting acetylene and, therefore, with each other due to the reversibility of the reaction. The existence of this equilibrium is demonstrated by transfer, under the condition of hydromagnesation 'HMgBr' from the vinylmagnesium compounds A/B to other acetylenes with regeneration of the starting acetylenes. Me3Si(BrMg)C = C(H)R (A) reversible Me3SiC = CR reversible Me3Si(H)C = C(MgBr)R (B). The position of the equilibrium between A and B was determined by deuterolysis and found to depend on the substituent, being 77:23 for R = n-C5H11 and 95:5 for R = cyclo-CH2C6H11 in diethyl ether. Reactions of the magnesium reagents A/B with electrophiles produce mixtures of linear (type A) and branched (type B) products. The ratios of regioisomeric products differ depending on the electrophile and the conditions (from 98:2 to 20:80). This is due to the preferential reaction of one of the regioisomers and to rapid equilibration.