tert-butyldimethyl((4-methylpent-4-en-1-yl)oxy)silane | 871840-51-6

• 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: tert-butyldimethyl((4-methylpent-4-en-1-yl)oxy)silane
• 英文别名: (4-methylpent-4-enyloxy)(tert-butyl)dimethylsilane；Tert-butyl(dimethyl)[(4-methyl-4-pentenyl)oxy]silane；tert-butyl-dimethyl-(4-methylpent-4-enoxy)silane
• CAS: 871840-51-6
• 化学式: C₁₂H₂₆OSi
• 分子量: 214.423
• InChiKey: CTXIPMCOYBSYTO-UHFFFAOYSA-N

物化性质

• 沸点：
  222.6±9.0 °C(Predicted)
• 密度：
  0.813±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：
  6
• 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：

  tert-butyldimethyl((4-methylpent-4-en-1-yl)oxy)silane 在 potassium dioxotetrahydroxoosmate(VI) Hydroquinone 1,4-phthalazinediyl diether 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 叔丁醇 为溶剂， 反应 48.0h， 以36.0 g的产率得到
  参考文献：
  名称：

  Pectenotoxin-2 Synthetic Studies. 3. Assessment of the Capacity for Stereocontrolled Cyclization To Form the Entire C1−C26 Subunit Based upon the Double Bond Geometry Across C15-C16

  摘要：

  Second-generation synthetic routes to enantiopure sulfone 21 and aldehyde 24 are described. The union of these two intermediates by means of a Julia-Kocienski coupling gave rise to a series of E-configured building blocks that did not prove amenable to transannular cyclization. Alternatively, when the C15-C16 double bond was introduced with Z-geometry by Wittig olefination, spontaneous closure to generate a tetrahydrofuran culminated an ensuing direct dihydroxylation step. The structural assignment to 35, undergirded by detailed H-1 and C-13 NMR studies, is consistent with proper transannular bonding so as to deliver the entire C1-C26 fragment of PTX2.

  DOI：

  10.1021/jo062513f
• 作为产物：
  描述：

  5-羟基-2-戊酮 在 咪唑 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 15.0h， 生成 tert-butyldimethyl((4-methylpent-4-en-1-yl)oxy)silane
  参考文献：
  名称：

  在二叔丁基亚甲硅烷基源的存在下，金属催化的均烯丙基醚到甲硅烷基甲基烯丙基硅烷的重排。

  摘要：

  [反应：见正文]在研究将二叔丁基亚甲硅烷基转移到宝石二取代的烯烃以形成硅环丙烷的范围时，我们发现了均空醚的空前反应。当在室温或更高温度下进行亚甲硅烷基转移时，两个二叔丁基亚甲硅烷基单元被引入分子中，并且碳主链发生了完全重排。该报告描述了这种独特反应的范围以及进行了机制研究的机制。

  DOI：

  10.1021/ol052456x

文献信息

• Enantiospecific Total Synthesis and Absolute Configuration Assignment of Chabrolobenzoquinone H
  作者：Stergios R. Rizos、Konstantinos A. Ouzounthanasis、Alexandros E. Koumbis

  DOI：10.1021/acs.joc.1c02634

  日期：2022.1.21

  meroditerpene metabolite with cytotoxic activity, is synthesized via a stereoselective Julia–Kocienski olefination between a chiral pool derived aliphatic PT-sulfone and a benzoquinone aldehyde partner. The latter was obtained via consecutive chain extension steps involving a Stille coupling and a stereospecific olefin cross-metathesis reaction followed by malonic ester synthesis and a Krapcho decarboxylation

  Chabrolobenzoquinone H ( 1 ) 是一种具有细胞毒活性的美二萜代谢物，通过手性池衍生的脂肪族 PT-砜和苯醌醛伴侣之间的立体选择性 Julia-Kocienski 烯化合成。后者是通过连续的扩链步骤获得的，包括 Stille 偶联和立体定向烯烃交叉复分解反应，然后是丙二酸酯合成和 Krapcho 脱羧。此外，这种全合成安全地确定了目标天然产物的绝对构型。
• Molecular Complexity via C–H Activation: A Dehydrogenative Diels–Alder Reaction
  作者：Erik M. Stang、M. Christina White

  DOI：10.1021/ja2059704

  日期：2011.9.28

  Traditionally, C-H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide-catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation.
• WENDER, P. A.;SNAPPER, M. L., TETRAHEDRON LETT., 28,(1987) N 20, 2221-2224
  作者：WENDER, P. A.、SNAPPER, M. L.

  DOI：——

  日期：——
• Metal-Catalyzed Rearrangement of Homoallylic Ethers to Silylmethyl Allylic Silanes in the Presence of a Di-<i>tert</i>-butylsilylene Source
  作者：Pamela A. Cleary、K. A. Woerpel

  DOI：10.1021/ol052456x

  日期：2005.11.1

  transfer to gem-disubstituted alkenes to form silacyclopropanes, we discovered an unprecedented reaction of homoallylic ethers. When silylene transfer was performed at room temperature or above, two di-tert-butylsilylene units were incorporated into the molecule, and complete rearrangement of the carbon backbone occurred. This report describes the scope of this unique reaction as well as the mechanistic

  [反应：见正文]在研究将二叔丁基亚甲硅烷基转移到宝石二取代的烯烃以形成硅环丙烷的范围时，我们发现了均空醚的空前反应。当在室温或更高温度下进行亚甲硅烷基转移时，两个二叔丁基亚甲硅烷基单元被引入分子中，并且碳主链发生了完全重排。该报告描述了这种独特反应的范围以及进行了机制研究的机制。
• Pectenotoxin-2 Synthetic Studies. 3. Assessment of the Capacity for Stereocontrolled Cyclization To Form the Entire C1−C26 Subunit Based upon the Double Bond Geometry Across C15-C16
  作者：Patrick D. O'Connor、Christopher K. Knight、Dirk Friedrich、Xiaowen Peng、Leo A. Paquette

  DOI：10.1021/jo062513f

  日期：2007.3.1

  Second-generation synthetic routes to enantiopure sulfone 21 and aldehyde 24 are described. The union of these two intermediates by means of a Julia-Kocienski coupling gave rise to a series of E-configured building blocks that did not prove amenable to transannular cyclization. Alternatively, when the C15-C16 double bond was introduced with Z-geometry by Wittig olefination, spontaneous closure to generate a tetrahydrofuran culminated an ensuing direct dihydroxylation step. The structural assignment to 35, undergirded by detailed H-1 and C-13 NMR studies, is consistent with proper transannular bonding so as to deliver the entire C1-C26 fragment of PTX2.