硅烷,(1,1-二甲基乙基)二甲基[[1-(2-丙烯基)-3-丁烯基]氧代]- | 139656-31-8

• 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
• 中文名称: 硅烷,(1,1-二甲基乙基)二甲基[[1-(2-丙烯基)-3-丁烯基]氧代]-
• 英文名称: tert-butyl(hepta-1,6-dien-4-yloxy)dimethylsilane
• 英文别名: 4-((tert-butyldimethylsilyl)oxy)-1,6-heptadiene；4-(tert-butyldimethylsilyloxy)hepta-1,6-diene；t-butyl(hepta-1,6-dien-4-yloxy)dimethylsilane；4-(tert-butyldimethylsiloxy)hepta-1,6-diene；4-tert-butyldimethylsiloxy-1,6-heptadiene；4-t-butyldimethylsilyloxy-1,6-heptadiene；4-(Tert-butyldimethylsiloxy)-1,6-heptadiene；tert-butyl-hepta-1,6-dien-4-yloxy-dimethylsilane
• CAS: 139656-31-8
• 化学式: C₁₃H₂₆OSi
• 分子量: 226.434
• InChiKey: MHOVRSGQQGEURJ-UHFFFAOYSA-N

物化性质

• 沸点：
  241.9±9.0 °C(Predicted)
• 密度：
  0.820±0.06 g/cm3(Predicted)
• 保留指数：
  1191.1

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  硅烷,(1,1-二甲基乙基)二甲基[[1-(2-丙烯基)-3-丁烯基]氧代]- 在 四丁基氟化铵 、 二(3-甲基丁烷-2-基)硼烷 作用下， 以 四氢呋喃 为溶剂， 生成 庚烷-1,4,7-三醇
  参考文献：
  名称：

  Synthesis of Glycerol Homologues

  摘要：

  A series of monoprotected glycerol homologues and triols were prepared in high overall yields (>90%) via the hydroboration-oxidation of the corresponding dienols. Hydroboration with disiamylborane and concomitant alkaline oxidation (NaOH, H2O2) was found to be a mild, high-yielding, and highly efficient method for the construction of a variety of glycerol homologues.

  DOI：

  10.1055/s-0033-1339185
• 作为产物：
  描述：

  叔丁基三甲基氯硅烷 、 1,6-庚二烯-4-醇 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以98%的产率得到硅烷,(1,1-二甲基乙基)二甲基[[1-(2-丙烯基)-3-丁烯基]氧代]-
  参考文献：
  名称：

  Synthesis of Glycerol Homologues

  摘要：

  A series of monoprotected glycerol homologues and triols were prepared in high overall yields (>90%) via the hydroboration-oxidation of the corresponding dienols. Hydroboration with disiamylborane and concomitant alkaline oxidation (NaOH, H2O2) was found to be a mild, high-yielding, and highly efficient method for the construction of a variety of glycerol homologues.

  DOI：

  10.1055/s-0033-1339185

文献信息

• Scope of the directed dihydroxylation: application to cyclic homoallylic alcohols and trihaloacetamides
  作者：Timothy J. Donohoe、Lee Mitchell、Michael J. Waring、Madeleine Helliwell、Andrew Bell、Nicholas J. Newcombe

  DOI：10.1039/b303081d

  日期：——

  The synthesis and directed dihydroxylation of a range of cyclic alkenes was investigated. Both homoallylic alcohols and homoallylic trihaloacetamides were found to be efficient directing groups, giving rise to good to excellent levels of remote asymmetric induction with OsO4–TMEDA. Interestingly, in all cases examined, trifluoroacetamides were found to be superior to trichloroacetamides as directing groups and an argument is presented which rationalises this observation.

  研究了一系列环状烯烃的合成及其定向双羟化反应。发现同烯丙醇和同烯丙三氟乙酰胺都是有效的导向基团，可以与OsO4–TMEDA体系一起实现良好的至优异的远程不对称诱导。有趣的是，在所有研究的情况下，三氟乙酰胺都被发现优于三氯乙酰胺作为导向基团，并提出了一个解释这一观察的合理论据。
• High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：EP1251135A3

  公开（公告）日：2004-01-02

  A method of preparing a catalyst of the formula comprising:reacting a compound of the formula (XX1MLnL1m)p with a phosphorane of the formula wherein:M is Os or Ru;R and R1 are either the same or different and are(a) hydrogen,(b) a group selected from C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C2-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, or C1-C20 alkylsulfinyl, or(c) one of the groups listed in (b) substituted with C1-C5 alkyl, halogen, C1-C5 alkoxy, unsubstituted phenyl, halogen substituted phenyl, C1-C5 alkyl substituted phenyl, or C1-C5 alkoxy substituted phenyl;R4, R5, and R6 are either the same or different and are each unsubstituted or substituted hydrocarbon wherein the hydrocarbon is selected from the group consisting of aryl, C1-C6 alkyl, C1-C6 alkoxy, and phenoxy and the hydrocarbon substitution is selected from the group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy, unsubstituted phenyl, halogen substituted phenyl, C1-C5 alkyl substituted phenyl, and C1-C5 alkoxy substituted phenyl;X and X1 are either the same or different and are any anionic ligand;L is any neutral electron donor;L1 is a trialkylphosphine ligand where at least one of the alkyl groups is a secondary alkyl or a cycloalkyl;n and m are independently 0-4, provided n+m=2, 3 or 4; andp is an integer equal to or greater than 1.

  制备配方催化剂的方法包括：将具有以下配方的化合物（XX1MLnL1m）与具有以下配方的磷烷反应：其中：M为Os或Ru；R和R1要么相同要么不同，且为(a) 氢，(b) 从C2-C20烯烃、C2-C20炔烃、C1-C20烷基、芳基、C1-C20羧酸酯、C2-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、芳氧基、C2-C20烷氧羰基、C1-C20烷硫基、C1-C20烷基磺酰基或C1-C20烷基亚磺酰基中选择的基团，或(c) 在(b)中列出的基团之一，其被C1-C5烷基、卤素、C1-C5烷氧基、未取代的苯基、卤素取代的苯基、C1-C5烷基取代的苯基或C1-C5烷氧基取代的苯基所取代；R4、R5和R6要么相同要么不同，且每个都是未取代或取代的碳氢化合物，其中碳氢化合物选自芳基、C1-C6烷基、C1-C6烷氧基和苯氧基组成的群，碳氢化合物取代选自卤素、C1-C3烷基、C1-C3烷氧基、未取代的苯基、卤素取代的苯基、C1-C5烷基取代的苯基和C1-C5烷氧基取代的苯基；X和X1要么相同要么不同，且为任何阴离子配体；L为任何中性电子给体；L1为三烷基膦配体，其中至少一个烷基是次烷基或环烷基；n和m独立地为0-4，条件是n+m=2、3或4；p为大于或等于1的整数。
• Divergent Synthesis of Aeruginosins Based on a C(sp³)H Activation Strategy
  作者：David Dailler、Grégory Danoun、Benjamin Ourri、Olivier Baudoin

  DOI：10.1002/chem.201501370

  日期：2015.6.22

  A general and scalable access to the aeruginosin family of marine natural products, exhibiting potent inhibitory activity against serine proteases, is reported. This was enabled by the strategic use of two recently implemented Pd‐catalyzed C(sp3)H activation reactions. The first method allowed us to obtain the common 2‐carboxy‐6‐hydroxyoctahydroindole (Choi) core of the target molecules on a large

  据报道，具有对丝氨酸蛋白酶的强抑制活性的海洋天然产品铜绿素家族普遍可扩展。这是通过战略性地利用两个最近实施的钯催化C（SP启用3）H活化反应。第一种方法使我们能够大规模获得目标分子的常见2-羧基-6-羟基八氢吲哚（Choi）核，而第二种方法则提供了快速多样的途径进入各种羟基苯基乳酸（Hpla）亚基，包括卤代亚基。这种独特的策略，加上片段偶联序列的优化，使得可以从手性库中合成出四种铜绿素酶，即98A–C和298A。其中，铜绿菌素298A以前所未有的大规模合成。此外，由于最终氢化步骤的微调，卤代铜绿蛋白酶98A和98C首次被合成。
• Alkylidene and Metalacyclic Complexes of Tungsten that Contain a Chiral Biphenoxide Ligand. Synthesis, Asymmetric Ring-Closing Metathesis, and Mechanistic Investigations
  作者：W. C. Peter Tsang、Kai C. Hultzsch、John B. Alexander、Peter J. Bonitatebus,、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1021/ja0210603

  日期：2003.3.1

  most cases and high % ee in asymmetric reactions. Exploration of the reaction between 2a and a stoichiometric amount of one desymmetrization substrate allowed two intermediate tungstacyclobutane complexes to be observed, in addition to the final and quite stable tungstacyclobutane complex formed in a reaction between the ring-closed product and a tungsten methylene complex. Reactions involving 13C labeled

  包含外消旋或对映体纯 (S) 形式的 3,3'-二叔丁基-5,5',6,6'-四甲基-1,1'-联苯-2,2'-的两种配合物二醇 (Biphen2-) 配体，W(NAr)(CHCMe2Ph)(Biphen) (2a) 和 W(NAr')(CHCMe2Ph)(Biphen) (2b) (Ar = 2,6-i-Pr2C6H3；Ar' = 2 ,6-Me2C6H3)，并被证明是几种有代表性的闭环反应的可行催化剂，在大多数情况下以良好的产率得到产物，在不对称反应中得到高 ee 百分比。除了在闭环产物与亚甲基钨配合物的反应中形成最终且非常稳定的钨环丁烷配合物之外，对 2a 与化学计量量的一种去对称化底物之间的反应的探索还允许观察到两种中间钨环丁烷配合物。
• Nickel-catalyzed cyclization of α,ω-dienes: formation vs. cleavage of C–C bonds
  作者：David Nečas、Matyáš Turský、Iva Tišlerová、Martin Kotora

  DOI：10.1039/b601631f

  日期：——

  A combination of a catalytic amount of a Ni–phosphine complex and triethylaluminium or chlorodiethylaluminium is able to selectively cyclize a number of 1,7-heptadienes to methylidene(methyl)cyclopentanes and cyclopentenes even in cases where the dienes are prone to deallylation.

  少量的镍-膦络合物和三乙基铝或氯二乙基铝的组合能够选择性地将多种1,7-七烯环化为美克烯（美克基）环戟烯和环戊烯，即使在这些烯烃易发生脱烯丙基反应的情况下也能有效进行。