(E)-2-butenyldimethylchlorosilane | 134870-77-2

• 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: (E)-2-butenyldimethylchlorosilane
• 英文别名: but-2-en-1-ylchlorodimethylsilane；(E)-Crotyldimethylchlorosilane；chlorocrotyldimethylsilane；[(E)-but-2-enyl]-chloro-dimethylsilane
• CAS: 134870-77-2
• 化学式: C₆H₁₃ClSi
• 分子量: 148.708
• InChiKey: ZIIOFRVBHAVTFG-SNAWJCMRSA-N

物化性质

• 沸点：
  142.6±9.0 °C(Predicted)
• 密度：
  0.883±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (E)-2-butenyldimethylchlorosilane 以 乙醚 为溶剂， 反应 0.08h， 生成 (E)-1,1-dimethyl-1-(2-buten-1-yl)silanol
  参考文献：
  名称：

  Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts

  摘要：

  The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 degrees C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (2)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

  DOI：

  10.1021/ja805951j
• 作为产物：
  描述：

  2-丁烯基溴 、 二氯二甲基硅烷 生成 (E)-2-butenyldimethylchlorosilane
  参考文献：
  名称：

  CHIHI, A.;WEBER, W. P., INORG. CHEM., 1981, 20, N 9, 2822-2824

  摘要：

  DOI：

文献信息

• Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair
  作者：Weidi Cao、Davin Tan、Richmond Lee、Choon-Hong Tan

  DOI：10.1021/jacs.7b13056

  日期：2018.2.7

  bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary

  报道了高度对映选择性双胍催化的酰基硅烷串联重排。通过在硅上添加氟化物来活化酰基硅烷以形成五配位阴离子硅酸盐中间体。然后硅酸盐经历烷基或芳基从硅原子迁移到相邻的羰基碳原子（1,2-阴离子重排），然后进行 [1,2]-布鲁克重排，以高产率提供具有优异对映选择性的仲醇（高达 95% ee）。α-甲硅烷基甲醇中间体的分离以及 DFT 计算表明，1,2-阴离子重排是通过双胍硅酸盐离子对发生的，这是立体确定步骤。然后通过随后的 [1,2]-布鲁克重排保留形成的手性中心而不发生反转。巴豆酰基硅烷顺利转化为高烯丙基线性巴豆醇，保留 E/Z 几何结构，未检测到支链醇。这清楚地表明 1,2-阴离子重排是通过三元而不是五元过渡态发生的。
• Dramatic Enhancement of Reactivity of Organosilicon Compounds Induced by Complexation of Bis(allyl)silanes with Fluoride Ion
  作者：Atsushi Shibato、Yoshifumi Itagaki、Eiji Tayama、Yasutoshi Hokke、Naoki Asao、Keiji Maruoka

  DOI：10.1016/s0040-4020(00)00458-0

  日期：2000.7

  New type of fluoride ion catalyzed allylation agent (1a, 1b), allenylation agent (9, 10), and alkynylation agent (17) can be successfully utilized for various carbonyl substrates. The rate acceleration is ascribable to the shift of equilibrium to the chelate complexes with Bu4NF by the favorable chelation of bis(silyl) compounds toward the fluoride ion. The 19F NMR spectrum (ethyl trifluoroacetate

  氟化物离子催化的烯丙基化剂（新类型1A，1B），allenylation剂（9，10），和炔基化剂（17）可以被成功地用于各种羰基的底物。通过双（甲硅烷基）化合物向氟离子的有利螯合，速率加速归因于平衡转移至具有Bu 4 NF的螯合物的螯合物。1a和Bu 4 NF的混合物在CDCl 3中的19 F NMR光谱（三氟乙酸乙酯为外标）在δ处显示两个峰-81.75和-77.67（积分比〜9：1）。大信号对应于Bu 4 NF的原始峰，小信号可能归因于1a和Bu 4 NF之间的螯合物[ B ] 。检查了双（巴甲基二甲基甲硅烷基）甲烷（7）与苯甲醛的氟离子介导的反应，并且选择性地获得了唯一的γ-加合物8。
• Fuerstner, Alois; Voigtlaender, David, Synthesis, 2000, # 7, p. 959 - 969
  作者：Fuerstner, Alois、Voigtlaender, David

  DOI：——

  日期：——
• AGOE, SEITIRO
  作者：AGOE, SEITIRO

  DOI：——

  日期：——
• CLARKE, MICHAEL P.;DAVIDSON, IAIN M. T., J. ORGANOMET. CHEM., 408,(1991) N, C. 149-156
  作者：CLARKE, MICHAEL P.、DAVIDSON, IAIN M. T.

  DOI：——

  日期：——