(E)-4(R)-(triethylsilyl)-2-pentene | 103981-02-8

• 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)-4(R)-(triethylsilyl)-2-pentene
• 英文别名: trans-4-triethylsilyl-2-pentene；(E)-4(S)-(triethylsilyl)-2-pentene；triethyl-[(E)-pent-3-en-2-yl]silane
• CAS: 103981-02-8
• 化学式: C₁₁H₂₄Si
• 分子量: 184.397
• InChiKey: BJRWWFRMJWSXMY-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.46
• 重原子数：
  12
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  特戊醛 、 (E)-4(R)-(triethylsilyl)-2-pentene 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以20%的产率得到(E)-(3R,4S)-2,2,4-trimethyl-5-hepten-3-ol
  参考文献：
  名称：

  Asymmetric synthesis catalyzed by chiral ferrocenylphosphine-transition metal complexes. 3. Preparation of optically active allylsilanes by palladium-catalyzed asymmetric Grignard cross-coupling

  摘要：

  DOI：

  10.1021/jo00370a006
• 作为产物：
  描述：

  三乙基硅烷 、 反-1,3-戊二烯 在 trimethylphosphinechromiumpentacarbonyl 作用下， 以 正己烷 为溶剂， 生成 (E)-4(R)-(triethylsilyl)-2-pentene 、 cis-1-triethylsilyl-2-pentene
  参考文献：
  名称：

  Photo-Induced Chromiumcarbonyl Catalyzed Hydrosilylation of Conjugated Dienes with Triethylsilane: The Solvent Effect

  摘要：

  共轭二烯（1,3-丁二烯，2-甲基-1,3-丁二烯，2,3-二甲基-1,3-丁二烯，反式-1,3-戊二烯）与三乙基硅烷的光催化氢硅烷化反应，使用Cr(CO)₅L（L = CO，P(CH₃)₃，P(OCH₃)₃，P(C₆H₅)₃，P(C₆H₁₁)₃，NC₅H₅）在两种非常不同的溶剂甲苯和四氢呋喃中进行研究，以与在正己烷中发现的结果进行比较。在甲苯中，光催化氢硅烷化产物与正己烷中的产物相同，唯一的例外是反式-1,3-戊二烯，它产生顺式-1-三乙基硅基-2-戊烯作为唯一产物。然而，在甲苯和正己烷中，每个前体配合物显示不同的催化活性。在甲苯中，1,3-丁二烯的氢硅烷化反应通常比正己烷中的快得多。在甲苯中使用Cr(CO)₆，Cr(CO)₅[P(CH₃)₃]或Cr(CO)₅[P(OCH₃)₃]，随着反应的进行，三乙基硅烷的转化几乎呈线性增加，表明活性催化剂在整个反应过程中保持稳定，类似于正己烷中的情况。虽然在正己烷中无法使用Cr(CO)₅[P(C₆H₅)₃]或Cr(CO)₅(NC₅H₅)实现1,3-丁二烯的氢硅烷化，但相同的前体配合物似乎在甲苯中是活跃的，尽管与使用Cr(CO)₅[P(CH₃)₃]或Cr(CO)₅[P(OCH₃)₃]获得的转化速率相比，转化速率要低得多。前体配合物Cr(CO)₅[P(C₆H₁₁)₃]在甲苯中和正己烷中均不显示催化活性。在四氢呋喃中，使用任何前体配合物都无法观察到1,3-丁二烯与三乙基硅烷的光催化氢硅烷化反应。通过在甲苯中使用Cr(CO)5[P(OCH3)3]作为催化剂，研究了共轭二烯在氢硅烷化中的相对反应性，得到与正己烷溶液中相同的反应性顺序：1,3-丁二烯 > 3-甲基-1,3-丁二烯 > 2,3-二甲基-1,3-丁二烯 > 反式-1,3-戊二烯。对于所有二烯烃，在甲苯中的氢硅烷化产物转化率均高于在正己烷中。

  DOI：

  10.1515/znb-2003-0707

文献信息

• Photocatalytic hydrosilylation of conjugated dienes with triethylsilane in the presence of Cr(CO)5L (L = CO, P(CH3)3, P(OCH3)3)
  作者：Saim Özkar、Vagif M. Akhmedov、Ceyhan Kayran

  DOI：10.1016/s0022-328x(96)06843-x

  日期：1997.4

  The effect of donor ligands on the chromium carbonyl photocatalysed hydrosilylation of 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, trans-1,3-pentadiene with triethylsilane was studied. Photocatalytic hydrosilylation of dienes conducted in the presence of Cr(CO)(5)L (L = P(CH3)(3) or P(OCH3)(3)) yields the cis-1,4-adducts, 1-triethylsilyl-2-butene derivatives, as the main products; these have been isolated by distillation or preparative GC and fully characterised by NMR spectroscopy. As with the photocatalytic hydrosilylation of dienes in the presence of Cr(CO)(6), we propose a mechanism which involves the initial conversion of Cr(CO)(5)L into fac-Cr(CO)(3)L(eta(4)-1,3-diene) followed by a further photolytic CO substitution by triethylsilane, forming a Cr(CO)(2)(H)(SiEt3)L(eta(4)-1,3-diene)intermediate. The addition of hydride to diene occurs reversibly to form an eta(3)-enyl ligand prior to the irreversible silyl transfer to the organic moiety. The 1,4-hydrosilylation adduct is then replaced by new substrates to complete the catalytic cycle. Cr(CO)SL complexes form active species which are much more stable than the one generated from CI(CO), in the absence of any donor ligands. Thus, introduction of an equimolar amount of donor ligand (trimethylphosphine or trimethylphosphite) increases the Life of the catalyst. This leads to the achievement of larger turn-over numbers (80 or 70) compared with the value of 30 for just Cr(CO)(6). Cr(CO)(5)L (L = P(C6H5)(3), P(C6H11)(3) or C5H5N) proved inactive in the attempted photocatalytic hydrosilylation of dienes.
• Asymmetric synthesis catalyzed by chiral ferrocenylphosphine-transition metal complexes. 3. Preparation of optically active allylsilanes by palladium-catalyzed asymmetric Grignard cross-coupling
  作者：Tamio Hayashi、Mitsuo Konishi、Yasuo Okamoto、Keiji Kabeta、Makoto Kumada

  DOI：10.1021/jo00370a006

  日期：1986.10
• Photo-Induced Chromiumcarbonyl Catalyzed Hydrosilylation of Conjugated Dienes with Triethylsilane: The Solvent Effect
  作者：Ceyhan Kayran、Saim Özkar、Vagif M. Akhmedov

  DOI：10.1515/znb-2003-0707

  日期：2003.7.1

  Photocatalytic hydrosilylation of conjugated dienes (1,3-butadiene, 2-methyl-1,3-butadiene, 2,3- dimethyl-1,3-butadiene, trans-1,3-pentadiene) with triethylsilane was studied by using Cr(CO)₅L (L = CO, P(CH₃)₃, P(OCH₃)₃, P(C₆H₅)₃, P(C₆H₁₁)₃, NC₅H₅) in two very different solvents, toluene and tetrahydrofuran, for comparison with the results found in n-hexane. In toluene, the photocatalytic hydrosilylation yields the same products as those in n-hexane, with the exception of trans- 1,3-pentadiene which gives cis-1-triethylsilyl-2-pentene as the sole product. However, each of the precursor complexes shows different catalytic activities in toluene and n-hexane. The hydrosilylation of 1,3-butadiene in toluene is, in general, significantly faster than that in n-hexane. By using Cr(CO)₆, Cr(CO)₅[P(CH₃)₃] or Cr(CO)₅[P(OCH₃)₃] in toluene, the conversion of triethylsilane increases almost linearly as the reaction proceeds, indicating the stability of the active catalyst throughout the reaction, similar to that in n-hexane. While no hydrosilylation of 1,3-butadiene could be achieved with Cr(CO)₅[P(C₆H₅)₃] or Cr(CO)₅(NC₅H₅) in n-hexane, the same precursor complexes appear to be active in toluene, though the conversion occurs at much lower rate compared to that obtained using Cr(CO)₅[P(CH₃)₃] or Cr(CO)₅[P(OCH₃)₃]. The precursor complex Cr(CO)₅[P(C₆H₁₁)₃] shows catalytic activity neither in toluene nor in n-hexane. No photocatalytic hydrosilylation of 1,3-butadiene with triethylsilane was observed in tetrahydrofuran by using any of the precursor complexes. The relative reactivity of conjugated dienes in the hydrosilylation was investigated by using triethylsilane in the presence of Cr(CO)5[P(OCH3)3] as catalyst in toluene, and the same reactivity order was obtained as in n-hexane solution: 1,3-butadiene > 3-methyl-1,3-butadiene > 2,3-dimethyl-1,3-butadiene > trans-1,3-pentadiene. For all of the dienes, one obtains higher conversion to hydrosilylated product in toluene than in n-hexane.

  共轭二烯（1,3-丁二烯，2-甲基-1,3-丁二烯，2,3-二甲基-1,3-丁二烯，反式-1,3-戊二烯）与三乙基硅烷的光催化氢硅烷化反应，使用Cr(CO)₅L（L = CO，P(CH₃)₃，P(OCH₃)₃，P(C₆H₅)₃，P(C₆H₁₁)₃，NC₅H₅）在两种非常不同的溶剂甲苯和四氢呋喃中进行研究，以与在正己烷中发现的结果进行比较。在甲苯中，光催化氢硅烷化产物与正己烷中的产物相同，唯一的例外是反式-1,3-戊二烯，它产生顺式-1-三乙基硅基-2-戊烯作为唯一产物。然而，在甲苯和正己烷中，每个前体配合物显示不同的催化活性。在甲苯中，1,3-丁二烯的氢硅烷化反应通常比正己烷中的快得多。在甲苯中使用Cr(CO)₆，Cr(CO)₅[P(CH₃)₃]或Cr(CO)₅[P(OCH₃)₃]，随着反应的进行，三乙基硅烷的转化几乎呈线性增加，表明活性催化剂在整个反应过程中保持稳定，类似于正己烷中的情况。虽然在正己烷中无法使用Cr(CO)₅[P(C₆H₅)₃]或Cr(CO)₅(NC₅H₅)实现1,3-丁二烯的氢硅烷化，但相同的前体配合物似乎在甲苯中是活跃的，尽管与使用Cr(CO)₅[P(CH₃)₃]或Cr(CO)₅[P(OCH₃)₃]获得的转化速率相比，转化速率要低得多。前体配合物Cr(CO)₅[P(C₆H₁₁)₃]在甲苯中和正己烷中均不显示催化活性。在四氢呋喃中，使用任何前体配合物都无法观察到1,3-丁二烯与三乙基硅烷的光催化氢硅烷化反应。通过在甲苯中使用Cr(CO)5[P(OCH3)3]作为催化剂，研究了共轭二烯在氢硅烷化中的相对反应性，得到与正己烷溶液中相同的反应性顺序：1,3-丁二烯 > 3-甲基-1,3-丁二烯 > 2,3-二甲基-1,3-丁二烯 > 反式-1,3-戊二烯。对于所有二烯烃，在甲苯中的氢硅烷化产物转化率均高于在正己烷中。

表征谱图