4-methyl-2,4-bis((trimethylsilyl)oxy)-1-pentene | 117201-96-4

• 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: 4-methyl-2,4-bis((trimethylsilyl)oxy)-1-pentene
• 英文别名: 2,2,4,4,8,8-Hexamethyl-6-methylene-3,7-dioxa-2,8-disilanonane；trimethyl-(2-methyl-4-trimethylsilyloxypent-4-en-2-yl)oxysilane
• CAS: 117201-96-4
• 化学式: C₁₂H₂₈O₂Si₂
• 分子量: 260.524
• InChiKey: GAGXTWXZSNHHOG-UHFFFAOYSA-N

物化性质

• 沸点：
  247.6±23.0 °C(Predicted)
• 密度：
  0.852±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.37
• 重原子数：
  16
• 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：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-methyl-2,4-bis((trimethylsilyl)oxy)-1-pentene 在 sodium tetrahydroborate 、 ytterbium(III) triflate hydrate 、 sodium acetate 、 三甲基乙酸酐 作用下， 以 甲醇 、 乙醇 、 水 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 96.0h， 生成 (E)-2-methylocta-5,7-diene-2,4-diol
  参考文献：
  名称：

  美亚霉素B的全合成

  摘要：

  Meayamycin B是目前最有效的剪接因子3b亚基1的调节剂，已有数十个研究小组使用。然而，由于冗长的合成方案，该天然产物类似物的电流供应受到限制。在这里，我们报道了通过开发和采用前手性烯酮的新型不对称还原以提供具有高对映选择性的烯丙基醇，该化合物更简洁，更具成本效益和更绿色的合成。除此反应外，该合成还突出显示了可扩展的Mukaiyama羟醛反应，Nicolaou型环氧化物开环反应，立体选择性Corey–Chaykovsky型反应和改良的Horner–Wadsworth–Emmons Z选择烯烃。我们还将讨论Z – Eα，β-不饱和酰胺形成过程中的异构化。meayamycin B的新合成包括最长线性序列中的11个步骤和总共24个步骤。

  DOI：

  10.1021/acs.joc.9b03370
• 作为产物：
  描述：

  三甲基氯硅烷 、 二丙酮醇 在 三乙胺 、 sodium iodide 作用下， 以 乙腈 为溶剂， 以82%的产率得到4-methyl-2,4-bis((trimethylsilyl)oxy)-1-pentene
  参考文献：
  名称：

  Chemoselective Activation of Trimethylsilyl Enol Ether Functionalities in the Presence of Silyl-Protected Alcohols by Trimethylsilyl-Nonaflyl Exchange

  摘要：

  具有三烷基硅烷保护的羟基的三甲基硅基烯醇醚，在二苯并-18-冠-6的催化量存在下，通过非氟硼酸丁烷-1-磺酰氟与氟化钾的共同作用，被转化为合成中有价值的含双功能烯丙基的壬酸酯。该方法已证明适用于结构多样的底物，这些底物具有各种三烷基硅烷保护的羟基，在反应过程中保持完整。

  DOI：

  10.1055/s-0030-1260207

文献信息

• Chemoselective Activation of Trimethylsilyl Enol Ether Functionalities in the Presence of Silyl-Protected Alcohols by Trimethylsilyl-Nonaflyl Exchange
  作者：Andrey Sheshenev、Ekaterina Boltukhina、Ilya Lyapkalo

  DOI：10.1055/s-0030-1260207

  日期：2011.11

  Trimethylsilyl enol ethers bearing trialkylsilyl-protected hydroxy groups were converted into synthetically valuable bifunctional alkenyl nonaflates under the action of nonafluorobutane-1-sulfonyl fluoride combined with potassium fluoride in the presence of catalytic amounts of dibenzo-18-crown-6. The methodology has been demonstrated for structurally diverse substrates possessing various trialkylsilyl-protected hydroxy groups which remained intact during the reaction course.

  具有三烷基硅烷保护的羟基的三甲基硅基烯醇醚，在二苯并-18-冠-6的催化量存在下，通过非氟硼酸丁烷-1-磺酰氟与氟化钾的共同作用，被转化为合成中有价值的含双功能烯丙基的壬酸酯。该方法已证明适用于结构多样的底物，这些底物具有各种三烷基硅烷保护的羟基，在反应过程中保持完整。
• SYNTHESIS OF FR901464 AND ANALOGS WITH ANTITUMOR ACTIVITY
  申请人：UNIVERSITY OF PITTSBURGH - OF THE COMMONWEALTH SYSTEM OF HIGHER EDUCATION

  公开号：US20150307512A1

  公开（公告）日：2015-10-29

  The present invention provides novel analogs of FR901464, as well as an improved methodology for preparing FR901464 and its analogs. These compounds display an anti-cancer activity and are candidates for therapies against a number of disease states associated with dysfunctional RNA splicing.

  本发明提供了FR901464的新型类似物，以及一种改进的制备FR901464及其类似物的方法。这些化合物表现出抗癌活性，是治疗与RNA剪接功能障碍相关的多种疾病状态的候选药物。
• Selective <i>O</i>‐Acylation of Enol Silyl Ethers with Acyl Fluorides Catalyzed by Fluoride Ions Derived from Potassium Fluoride and 18‐Crown‐6
  作者：Norio Sakai、Kota Watanabe、Haruka Mori、Yuki Maegawa、Ryuki Takeuchi、Yohei Ogiwara、Kento Ishida

  DOI：10.1002/open.202300300

  日期：——

  Fluoride ions derived from potassium fluoride and 18-crown-6 efficiently catalyzed the selective O-acylation of a variety of enol silyl ethers with aromatic and aliphatic acyl fluorides to produce unique enol ester derivatives.

  源自氟化钾和18-crown-6的氟离子有效催化多种烯醇甲硅烷基醚与芳香族和脂肪族酰氟发生选择性O-酰化反应，生成独特的烯醇酯衍生物。
• A General and Versatile Method for CC Cross-Coupling Synthesis of Conjugated Enynes: One-Pot Sequence Starting from Carbonyl Compounds
  作者：Ilya M. Lyapkalo、Michael A. K. Vogel

  DOI：10.1002/anie.200504594

  日期：2006.6.12
• Chemistry of dioxenium cations. Synthetic and mechanistic studies on the stereocontrolled formation of tetrahydropyrans from homoallylic alcohols and ortho esters
  作者：Francoise Perron-Sierra、Michele A. Promo、Van A. Martin、Kim F. Albizati

  DOI：10.1021/jo00021a043

  日期：1991.10

  Despite their long history, dioxenium cations are underutilized reactive synthetic intermediates. It was found that ortho esters and homoallylic alcohols in the presence of Lewis acids provide 4-heterosubstituted pyranosides in a stereoselective manner. The mechanistic course of events was supported by control experiments and synthesis of a putative mixed ortho ester intermediate which exhibited identical reactivity. A transition state for termination of the dioxenium cation-olefin cyclization is proposed, involving intramolecular delivery of chloride by a coordinated tin species. Structure-reactivity relationships indicate that a cation-stabilizing substituent (alkyl or alkoxy) at the internal position of the olefin is required for cyclization. A variety of 3-alkyl-substituted homoallylic alcohols cyclize cleanly to substituted 2-alkoxytetrahydropyrans in good yield. beta-silyloxy silyl enol ethers were found to smoothly provide 4-oxotetrahydropyranosides when subjected to the same reaction conditions. For these substrates, the course of the cyclization proceeds in a different manner involving a rapid intermolecular Mukaiyama aldol condensation followed by transacetalization.