triisopropyl((3-methylbut-3-en-1-yl)oxy)silane

• 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: triisopropyl((3-methylbut-3-en-1-yl)oxy)silane
• 英文别名: 3-Methylbut-3-enoxy-tri(propan-2-yl)silane
• 化学式: C₁₄H₃₀OSi
• 分子量: 242.477
• InChiKey: NXZRDINVTWEBNC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  triisopropyl((3-methylbut-3-en-1-yl)oxy)silane 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二乙酯 、 二氯乙基铝 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 癸烷 、 二氯甲烷 为溶剂， 反应 218.5h， 生成 ((2S,3S)-3-(2-methylene-4-((triisopropylsilyl)oxy)butyl)oxiran-2-yl)methanol
  参考文献：
  名称：

  Exploratory studies toward the synthesis of the peroxylactone unit of plakortolides

  摘要：

  Our efforts in construction the 1,2-dioxane ring of plakortolides through two approaches are described. The first one involved as a key step an acid catalyzed 6-endo ring closure of beta-hydroperoxy trans-epoxides directed by a vinyl group adjacent to the epoxide function. By this route, an advanced intermediate of plakortolides was obtained in six steps and 35% overall yield. The second approach featured a 1,2-dioxane ring forming by a double opening of bis-epoxides by ethereal hydrogen peroxide. This reaction did not proceed in the expected sense and exclusive formation of hydroperoxy tetrahydropyran derivatives was observed via a tandem oxacyclization-hydroperoxidation sequence. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.024
• 作为产物：
  描述：

  三甲基铝 、 but-3-ynyloxy-triisopropyl-silane 在 rac-ethylenebis(1-indenyl)zirconium(IV) chloride methylalumoxane 、 盐酸 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以82%的产率得到triisopropyl((3-methylbut-3-en-1-yl)oxy)silane
  参考文献：
  名称：

  Controlling Regiochemistry in Negishi Carboaluminations. Fine Tuning the Ligand on Zirconium

  摘要：

  The species on the zirconocene catalyst is changed from two Cp's to the Brintzinger ligand and catalytic amounts of MAO are used to usually effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene.

  DOI：

  10.1021/ja065769b

文献信息

• Synthesis of Dienyl Ketones via Palladium(II)-Catalyzed Direct Cross-Coupling Reactions between Simple Alkenes and Vinyl Ketones: Application to the Synthesis of Vitamin A1 and Bornelone
  作者：Xiang Zhang、Min Wang、Ming-Xin Zhang、Yun-He Xu、Teck-Peng Loh

  DOI：10.1021/ol402692t

  日期：2013.11

  An efficient and general method for the synthesis of conjugated dienyl ketones via palladium(II) acetate catalyzed direct cross-coupling between simple alkenes and vinyl ketones is reported. This method has been successfully applied for the synthesis of Vitamin A1 and bornelone.

  报道了通过乙酸钯（II）催化的简单烯烃与乙烯基酮之间的直接交叉偶联来合成共轭二烯基酮的有效且通用的方法。该方法已成功应用于维生素A1和冰片的合成。
• Palladium-Catalyzed Cross-Coupling of Unactivated Alkenes with Acrylates: Application to the Synthesis of the C13-C21 Fragment of Palmerolide A
  作者：Zhen-Kang Wen、Yun-He Xu、Teck-Peng Loh

  DOI：10.1002/chem.201201806

  日期：2012.10.15

  Diene to meet: A palladium‐catalyzed cross‐coupling reaction between alkyl‐substituted olefins and acrylates gives the corresponding butadienes in moderate yield and stereoselectivity. This atom‐economical reaction, which forms C–C bonds, tolerates a wide range of allylic and homoallylic alcohols, and acrylates (see scheme; TIPS =triisopropylsilyl). The methodology was applied to the synthesis of the

  满足的二烯：烷基取代的烯烃与丙烯酸酯之间的钯催化交叉偶联反应以中等收率和立体选择性提供了相应的丁二烯。这种形成C- C键的原子经济反应可耐受各种烯丙基和均烯丙基醇以及丙烯酸酯（请参见方案； TIPS =三异丙基甲硅烷基）。该方法应用于棕榈油内酯A的C13–C21片段的合成。
• In Situ Synthesis and Applications for Polyinterhalides Based on BrCl
  作者：Benjamin Schmidt、Sebastian Ponath、Johannes Hannemann、Patrick Voßnacker、Karsten Sonnenberg、Mathias Christmann、Sebastian Riedel

  DOI：10.1002/chem.202001267

  日期：2020.11.26

  The use of neat BrCl in organic and inorganic chemistry is limited due to its gaseous aggregate state and especially its decomposition into Cl2 and Br2. The stabilization of BrCl in form of reactive ionic liquids via a novel in situ synthesis route shifts this equilibrium drastically to the BrCl side, which leads to safer and easier‐to‐handle interhalogenation reagents. Furthermore, the crystalline

  由于其气态聚集态，尤其是分解成Cl 2和Br 2，纯BrCl在有机和无机化学中的使用受到限制。通过一种新颖的原位合成途径以反应性离子液体的形式稳定 BrCl，使这种平衡急剧向 BrCl 侧移动，从而产生更安全、更易于处理的卤化试剂。此外，还合成了迄今为止未知的[Cl(BrCl) 2 ] -和[Cl(BrCl) 4 ] -阴离子的晶体衍生物，并通过单晶X射线衍射(XRD)、拉曼和红外光谱进行了表征。作为量子化学计算。
• Exploratory studies toward the synthesis of the peroxylactone unit of plakortolides
  作者：Bogdan Barnych、Jean-Michel Vatèle

  DOI：10.1016/j.tet.2012.03.024

  日期：2012.5

  Our efforts in construction the 1,2-dioxane ring of plakortolides through two approaches are described. The first one involved as a key step an acid catalyzed 6-endo ring closure of beta-hydroperoxy trans-epoxides directed by a vinyl group adjacent to the epoxide function. By this route, an advanced intermediate of plakortolides was obtained in six steps and 35% overall yield. The second approach featured a 1,2-dioxane ring forming by a double opening of bis-epoxides by ethereal hydrogen peroxide. This reaction did not proceed in the expected sense and exclusive formation of hydroperoxy tetrahydropyran derivatives was observed via a tandem oxacyclization-hydroperoxidation sequence. (C) 2012 Elsevier Ltd. All rights reserved.
• Controlling Regiochemistry in Negishi Carboaluminations. Fine Tuning the Ligand on Zirconium
  作者：Bruce H. Lipshutz、Tom Butler、Asher Lower

  DOI：10.1021/ja065769b

  日期：2006.12.1

  The species on the zirconocene catalyst is changed from two Cp's to the Brintzinger ligand and catalytic amounts of MAO are used to usually effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene.