triethyl(hex-5-en-2-yloxy)silane | 4848-07-1

• 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: triethyl(hex-5-en-2-yloxy)silane
• 英文别名: 2-Triaethylsiloxy-hexen-(5)；triethyl-(1-methyl-pent-4-enyloxy)-silane；5-triethylsilanyloxy-hex-1-ene；CH2=CH(CH2)2CH(Me)OSiEt3
• CAS: 4848-07-1
• 化学式: C₁₂H₂₆OSi
• 分子量: 214.423
• InChiKey: OQEGDMCGFUEYPD-UHFFFAOYSA-N

物化性质

• 沸点：
  86 °C(Press: 5 Torr)
• 密度：
  0.811±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  14
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  triethyl(hex-5-en-2-yloxy)silane 在 盐酸 作用下， 生成 5-己烯-2-醇
  参考文献：
  名称：

  Komarov,N.V.; Roman,V.K., Journal of general chemistry of the USSR, 1965, vol. 35, p. 2008 - 2010

  摘要：

  DOI：
• 作为产物：
  描述：

  三乙基硅烷 、 5-已烯-2-酮 在 fluorotris(pentafluorophenyl)phosphonium tetrakis(pentafluorophenyl)borate 作用下， 反应 6.0h， 以95%的产率得到triethyl(hex-5-en-2-yloxy)silane
  参考文献：
  名称：

  亲电子Ph阳离子催化的酮，亚胺和腈的氢化硅烷化：官能团的选择性和机理考虑

  摘要：

  亲电子phospho盐，[（C 6 F 5）3 PF] [B（C 6 F 5）4 ]，在室温下催化酮，亚胺和腈的有效氢化硅烷化。在这种催化剂的存在下，向腈中加入一当量的氢硅烷会产生甲硅烷基苯丙胺产物，而添加第二当量的甲硅烷会产生相应的二甲硅烷基胺。[（C 6 F 5）3 PCl] [B（C 6 F 5）4 ]和[（C 6 F 5）3 PBr] [B（C 6 F 5）4也被合成并作为催化剂测试。竞争实验表明，该反应对以下官能团表现出选择性，其优先顺序为：酮>腈>亚胺>烯烃。计算研究表明，该反应机理涉及通过与with中心的相互作用而使SiH键初始活化。然后，活化的络合物协同作用于不饱和底物上。

  DOI：

  10.1002/chem.201406356

文献信息

• Recyclable catalysts methods of making and using the same
  申请人：Brookhaven Science Associates, LLC

  公开号：US07005525B2

  公开（公告）日：2006-02-28

  Organometallic complexes are provided, which include a catalyst containing a transition metal, a ligand and a component having the formula GArF. ArF is an aromatic ring system selected from phenyl, naphthalenyl, anthracenyl, fluorenyl, or indenyl. The aromatic ring system has at least a substituent selected from fluorine, hydrogen, hydrocarbyl or fluorinated hydrocarbyl, G is substituted or unsubstituted (CH2)n or (CF2)n, wherein n is from 1 to 30, wherein further one or more CH2 or CF2 groups are optionally replaced by NR, PR, SiR2, BR, O or S, or R is hydrocarbyl or substituted hydrocarbyl, GArF being covalently bonded to either said transition metal or said ligand of said catalyst, thereby rendering said cationic organometallic complex liquid. The catalyst of the organometallic complex can be [CpM(CO)2(NHC)Lk]+A−, wherein M is an atom of molybdenum or tungsten, Cp is substituted or unsubstituted cyclopentadienyl radical represented by the formula [C5Q1Q2Q3Q4Q5], wherein Q1 to Q5 are independently selected from the group consisting of H radical, GArF C1-20 hydrocarbyl radical, substituted hydrocarbyl radical, substituted hydrocarbyl radical substituted by GArF, halogen radical, halogen-substituted hydrocarbyl radical, —OR, —C(O)R′, —CO2R′, —SiR′3 and —NR′R″, wherein R′ and R″ are independently selected from the group consisting of H radical, C1-20 hydrocarbyl radical, halogen radical, and halogen-substituted hydrocarbyl radical, wherein said Q1 to Q5 radicals are optionally linked to each other to form a stable bridging group, NHC is any N-heterocyclic carbene ligand, L is either any neutral electron donor ligand, wherein k is a number from 0 to 1 or L is an anionic ligand wherein k is 2, and A− is an anion. Processes using the organometallic complexes as catalysts in catalytic reactions, such as for example, the hydrosilylation of aldehydes, ketones and esters are also provided.

  提供了含有过渡金属、配体和公式为GArF的组分的有机金属配合物催化剂。ArF是从苯基、萘基、蒽基、芴基或茚基中选择的芳香环系统。芳香环系统至少有一个氟、氢、烃基或氟代烃基的取代基。G是取代或未取代的(CH2)n或(CF2)n，其中n为1至30之间的数值。进一步地，一个或多个CH2或CF2基团可以选择性地被NR、PR、SiR2、BR、O或S替换，或R是烃基或取代烃基。因此，GArF与所述过渡金属或所述催化剂的配体之一共价键合，从而使所述阳离子有机金属配合物液态化。该有机金属配合物的催化剂可以是[CpM(CO)2(NHC)Lk]+A−，其中M是钼或钨原子，Cp是由公式[C5Q1Q2Q3Q4Q5]表示的取代或未取代的环戊二烯基基团，其中Q1至Q5独立地选择自由基H、GArF C1-20烃基基团、取代烃基基团、由GArF取代的取代烃基基团、卤素基团、卤素取代的烃基基团、—OR、—C(O)R′、—CO2R′、—SiR′3和—NR′R″的群，其中R′和R″独立地选择自由基H、C1-20烃基基团、卤素基团和卤素取代的烃基基团，所述Q1至Q5基团可以选择性地连接在一起形成稳定的桥接基团，NHC是任何N-杂环卡宾配体，L是任何中性电子给体配体，其中k为0至1的数字，或L是一个带负电的配体，其中k为2，A−是一个阴离子。还提供了使用有机金属配合物作为催化剂进行催化反应的过程，例如醛、酮和酯的氢硅化反应。
• Controlled Hydrosilylation of Carbonyls and Imines Catalyzed by a Cationic Aluminum Alkyl Complex
  作者：Jürgen Koller、Robert G. Bergman

  DOI：10.1021/om2008277

  日期：2012.4.9

  The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I-3] (3) revealed the preference of Al for a tetrahedral coordination environment and the versatility of the Tp* ligand in stabilizing Al in bi- and tridentate coordination modes. [Tp*AlMe][MeB(C6F5)(3)] (2) is highly active toward the hydrosilylation of a wide variety of carbonyls and imines, thus providing an inexpensive and versatile alternative to late transition metal catalysts.
• Komarov,N.V.; Roman,V.K., Journal of general chemistry of the USSR, 1965, vol. 35, p. 2008 - 2010
  作者：Komarov,N.V.、Roman,V.K.

  DOI：——

  日期：——
• Hydrosilylation of Ketones, Imines and Nitriles Catalysed by Electrophilic Phosphonium Cations: Functional Group Selectivity and Mechanistic Considerations
  作者：Manuel Pérez、Zheng-Wang Qu、Christopher B. Caputo、Vitali Podgorny、Lindsay J. Hounjet、Andreas Hansen、Roman Dobrovetsky、Stefan Grimme、Douglas W. Stephan

  DOI：10.1002/chem.201406356

  日期：2015.4.20

  efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine. [(C6F5)3PCl][B(C6F5)4] and [(C6F5)3PBr][B(C6F5)4] are also synthesised and tested as catalysts. Competition experiments demonstrate that the

  亲电子phospho盐，[（C 6 F 5）3 PF] [B（C 6 F 5）4 ]，在室温下催化酮，亚胺和腈的有效氢化硅烷化。在这种催化剂的存在下，向腈中加入一当量的氢硅烷会产生甲硅烷基苯丙胺产物，而添加第二当量的甲硅烷会产生相应的二甲硅烷基胺。[（C 6 F 5）3 PCl] [B（C 6 F 5）4 ]和[（C 6 F 5）3 PBr] [B（C 6 F 5）4也被合成并作为催化剂测试。竞争实验表明，该反应对以下官能团表现出选择性，其优先顺序为：酮>腈>亚胺>烯烃。计算研究表明，该反应机理涉及通过与with中心的相互作用而使SiH键初始活化。然后，活化的络合物协同作用于不饱和底物上。