三(三甲基硅基)氧乙烯基硅烷 | 861445-91-2

• 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: 三(三甲基硅基)氧乙烯基硅烷
• 中文别名: 三（三甲基硅基）氧乙烯基硅烷
• 英文名称: tris(trimethylsilyl)-vinyloxy-silane
• 英文别名: Tris(trimethylsilyl)silyl vinyl ether；ethenoxy-tris(trimethylsilyl)silane
• CAS: 861445-91-2
• 化学式: C₁₁H₃₀OSi₄
• 分子量: 290.701
• InChiKey: WPZQENSANSNYSI-UHFFFAOYSA-N

物化性质

• 熔点：
  51-61 °C
• 闪点：
  78 °C

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 危险品标志：
  F,Xi
• 危险类别码：
  R36/37/38,R11
• 危险品运输编号：
  UN 1325 4.1/PG 3
• 安全说明：
  S26,S36/37

反应信息

• 作为反应物：
  描述：

  三(三甲基硅基)氧乙烯基硅烷 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 双三氟甲烷磺酰亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (2R)-2-[(2R,4S)-4-[tert-butyl(dimethyl)silyl]oxy-2-tris(trimethylsilyl)silyloxypentyl]-2,3-dihydropyran-6-one
  参考文献：
  名称：

  “Super Silyl” Group for Diastereoselective Sequential Reactions:  Access to Complex Chiral Architecture in One Pot

  摘要：

  We have shown that the tris(trimethylsilyl)silyl (TTMSS) silyl enol ether of acetaldehyde undergoes aldehyde cross-aldol reactions with high selectivity and the extremely low catalyst loading (0.05 mol % of HNTf2) allows for one-pot sequential reactions where acidic or basic nucleophiles can be subsequently added. Various ketone-derived silyl enol ethers, Grignard reagents, and dienes succeeded, generating relatively complex molecular architectures in a single step. This represents the first case where, in a single pot, highly acidic conditions followed by very basic conditions were tolerated to give products with high diastereoselectivities and good yields.

  DOI：

  10.1021/ja0693542
• 作为产物：
  描述：

  三(三甲基硅基)硅烷 、 乙醛 在 三氟甲磺酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以72%的产率得到三(三甲基硅基)氧乙烯基硅烷
  参考文献：
  名称：

  Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction

  摘要：

  The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.

  DOI：

  10.1021/ja054725k

文献信息

• Ketone Super Silyl Enol Ethers in Sequential Reactions:  Diastereoselective Generation of Tertiary Carbinols in One Pot
  作者：Matthew B. Boxer、Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1021/ja7102586

  日期：2008.2.6

  Ketone super silyl enol ethers are shown to be excellent nucleophiles in the Mukaiyama aldol reaction as well as in sequential one-pot diastereoselective reactions. High yields and diastereoselectivities are obtained with a variety of silyl enol ether/aldehyde/Grignard combinations. The utility of this reaction is exemplified in a one-pot 4-component reaction generating two secondary and one tertiary

  酮超级甲硅烷基烯醇醚在向山羟醛反应以及连续的一锅非对映选择性反应中显示为优异的亲核试剂。使用各种甲硅烷基烯醇醚/醛/格氏组合可获得高产率和非对映选择性。该反应的效用以一步生成两种仲醇和一种叔醇的一锅四组分反应为例。
• Controlling stereochemistry in polyketide synthesis: 1,3- vs. 1,2-asymmetric induction in methyl ketone aldol additions to β-super siloxy aldehydes
  作者：Patrick B. Brady、Brian J. Albert、Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1039/c3sc51183a

  日期：——

  The aldol addition of methyl ketones to β-siloxy and α-methyl β-siloxy aldehydes is described. Careful control of mechanistically distinct aldol reactions leverages 1,2- and 1,3-asymmetric induction, selectively forming syn and anti aldol adducts with excellent diastereocontrol. Experimental and theoretical investigations have provided insight to the factors governing diastereoselectivity.

  描述了将甲基酮醛醇缩合至β-甲硅烷氧基和α-甲基β-甲硅烷氧基醛。仔细控制机械上不同的羟醛反应可利用1,2-和1,3-不对称诱导，选择性地形成顺式和反式羟醛加合物，并具有出色的非对映控制性。实验和理论研究为控制非对映选择性的因素提供了见识。
• Confinement-Controlled, Either <i>syn</i>- or <i>anti</i>-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes
  作者：Tynchtyk Amatov、Nobuya Tsuji、Rajat Maji、Lucas Schreyer、Hui Zhou、Markus Leutzsch、Benjamin List

  DOI：10.1021/jacs.1c07447

  日期：2021.9.15

  Protected aldols (i.e., true aldols derived from aldehydes) with either syn- or anti- stereochemistry are versatile intermediates in many oligopropionate syntheses. Traditional stereoselective approaches to such aldols typically require several nonstrategic operations. Here we report two highly enantioselective and diastereoselective catalytic Mukaiyama aldol reactions of the TBS- or TES- enolsilanes

  具有顺式或反式立体化学的受保护醛醇（即来自醛的真正醛醇）是许多低聚丙酸酯合成中的通用中间体。这种醛醇的传统立体选择性方法通常需要几个非战略性操作。在这里，我们报告了丙醛的 TBS-或 TES-烯醇硅烷与芳香醛的两种高度对映选择性和非对映选择性催化 Mukaiyama 羟醛反应。我们的反应以催化剂控制的方式直接提供有价值的甲硅烷基保护的丙醛醛醇，无论是合成还是反异构体。我们已经确定了一种特权 IDPi 催化剂基序，该基序专为控制这些醛醇化反应而设计，具有出色的选择性。我们展示了 IDPi 催化剂内核中的单原子修饰，用CF 2 H 基团替换 CF 3基团，如何导致醛的对映面分化发生戏剧性的转变。这种显着效果的起源归因于通过 CF 2 H 基团的非常规 C-H 氢键使催化腔变紧。
• Remarkable Tris(trimethylsilyl)silyl Group for Diastereoselective [2 + 2] Cyclizations
  作者：Matthew B. Boxer、Hisashi Yamamoto

  DOI：10.1021/ol0512334

  日期：2005.7.1

  [reaction: see text] Diastereoselective [2 + 2] cyclizations of aldehyde- and ketone-derived silyl enol ethers with acrylates is described. The use of the tris(trimethylsilyl)silyl group allows for unprecedented reactivity, yields, and selectivity for these cyclizations. The presence of silicon-silicon bonds proved to be important for this transformation, where typical silyl groups (TBS and TIPS) failed

  [反应：见正文]描述了醛和酮衍生的甲硅烷基烯醇醚与丙烯酸酯的非对映选择性[2 + 2]环化反应。三（三甲基甲硅烷基）甲硅烷基的使用为这些环化反应提供了空前的反应性，产率和选择性。事实证明，硅-硅键的存在对于这种转化非常重要，在这种转化中，典型的甲硅烷基（TBS和TIPS）无法提供任何所需的产物。庞大的双（2,6-二苯基苯氧基）三氟化铝催化剂对于高非对映选择性至关重要。
• Rapid Total Syntheses Utilizing “Supersilyl” Chemistry
  作者：Brian J. Albert、Yousuke Yamaoka、Hisashi Yamamoto

  DOI：10.1002/anie.201007210

  日期：2011.3.7

  In short order: The shortest total syntheses of natural product EBC‐23 (see scheme, PMB=para‐methoxybenzyl, TMS=trimethylsilyl) and a polymethoxy‐1‐alkene to date have been accomplished in just ten total steps each from commercially available chemicals. The syntheses took advantage of highly diastereoselective supersilyl‐directed cascade polyaldol reactions.

  短期内：迄今为止最短的天然产物 EBC-23（见方案，PMB=对甲氧基苄基，TMS=三甲基甲硅烷基）和聚甲氧基 1-烯烃的全合成仅在十个总步骤中完成，每个步骤均来自市售化学品. 该合成利用了高度非对映选择性的超甲硅烷基引导的级联聚醛醇反应。