Et2CHOSiMe2Ph | 609768-97-0

• 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: Et2CHOSiMe2Ph
• 英文别名: dimethyl-pentan-3-yloxy-phenylsilane
• CAS: 609768-97-0
• 化学式: C₁₃H₂₂OSi
• 分子量: 222.403
• InChiKey: HLKZSPGONAVUMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  、 、 、 、 、 Et2CHOSiMe2Ph 、 、 、 triethyl(hex-5-en-2-yloxy)silane 、 triethyl(1-phenylethoxy)silane 、 (1-para-fluorophenylethoxy)triethylsilane 、 、 CH3CH=CH(CH2)2OSiEt3 、 聚合甲醛 、 、 、 生成 triethyl(1-ethyl-n-propoxy)silane
  参考文献：
  名称：

  Recyclable catalysts methods of making and using the same

  摘要：

  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。

  公开号：

  US07005525B2
• 作为产物：
  描述：

  3-dimethylphenylsiloxy-1,4-pentadiene 在 氢气 、 (+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯 作用下， 以 1,2-二氯乙烷 为溶剂， 21.0 ℃ 、162.13 kPa 条件下， 反应 0.25h， 生成 Et2CHOSiMe2Ph 、 、 ((S)-1-Ethyl-allyloxy)-dimethyl-phenyl-silane
  参考文献：
  名称：

  非共轭二烯在铑催化的还原反应中的立体选择性

  摘要：

  Abstractmagnified imageThe stereochemical course of rhodium‐catalysed addition of hydrogen and catecholborane to bicyclo[2.2.1]heptadiene, and of hydrogen to a range of cyclic dienes has been analysed. For hydroboration, the overall catalytic reaction possesses exo‐selectivity, but the initial step is endo‐selective. For hydrogenation (deuteration), the first step may occur with either exo‐ or endo‐ selectivity, depending on the structure of the diene. This enables a distinction to be made between pathways involving prior dissociation of the diene, and direct addition to the complexed diene without full dissociation. The relative ease of hydrogenation of the first and second double bonds varies markedly with reactant structure, and also depends on the choice of catalyst ligands. For dicyclopentadiene, hydrogenation of the cyclopentene double bond is accompanied by rapid alkene isomerisation, as revealed by deuterium addition. The asymmetric hydrogenation of acyclic skipped meso‐dienes is reported, demonstrating control of relative rates of the two sequential steps, with ees of up to 53% after the first reduction.

  DOI：

  10.1002/adsc.200900013

文献信息

• Stereoselectivity in the Rhodium-Catalysed Reductions of Non-Conjugated Dienes
  作者：Bao Nguyen、John M. Brown

  DOI：10.1002/adsc.200900013

  日期：2009.6

  Abstractmagnified imageThe stereochemical course of rhodium‐catalysed addition of hydrogen and catecholborane to bicyclo[2.2.1]heptadiene, and of hydrogen to a range of cyclic dienes has been analysed. For hydroboration, the overall catalytic reaction possesses exo‐selectivity, but the initial step is endo‐selective. For hydrogenation (deuteration), the first step may occur with either exo‐ or endo‐ selectivity, depending on the structure of the diene. This enables a distinction to be made between pathways involving prior dissociation of the diene, and direct addition to the complexed diene without full dissociation. The relative ease of hydrogenation of the first and second double bonds varies markedly with reactant structure, and also depends on the choice of catalyst ligands. For dicyclopentadiene, hydrogenation of the cyclopentene double bond is accompanied by rapid alkene isomerisation, as revealed by deuterium addition. The asymmetric hydrogenation of acyclic skipped meso‐dienes is reported, demonstrating control of relative rates of the two sequential steps, with ees of up to 53% after the first reduction.
• 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。