(E)-crotyltrifluorosilane | 114067-35-5

• 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: (E)-crotyltrifluorosilane
• 英文别名: Silane, 2-butenyltrifluoro-；[(E)-but-2-enyl]-trifluorosilane
• CAS: 114067-35-5
• 化学式: C₄H₇F₃Si
• 分子量: 140.18
• InChiKey: CJXYVJHFYSFWFK-NSCUHMNNSA-N

物化性质

• 沸点：
  53.2±9.0 °C(Predicted)
• 密度：
  0.999±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-crotyltrifluorosilane 在 十二/十四烷基二甲基氧化胺 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 20.0h， 生成 巴豆醇
  参考文献：
  名称：

  Oxidative SIC bond cleavage of organotrifluorosilanes involving organic-group migration from hypercoordinate silicon to oxygen

  摘要：

  DOI：

  10.1016/s0040-4039(00)99364-x
• 作为产物：
  描述：

  2-丁烯-1-基(三氯)硅烷 在 三氟化锑 作用下， 以94%的产率得到(E)-crotyltrifluorosilane
  参考文献：
  名称：

  （E）-和（Z）-巴豆基三氟硅烷的立体异构合成和醛的高度立体选择性烯丙基化

  摘要：

  制备了立体均相的（E）-和（Z）-巴豆基三氟硅烷，并将其分别用于在氟离子存在下由醛类从醛类中高非对映选择性地分别合成苏-和-β-甲基-甲基烯丙基醇。讨论了反应机理。

  DOI：

  10.1016/s0040-4039(01)80370-1

文献信息

• Stereochemistry of the Allylation and Crotylation Reactions of α-Methyl-β-hydroxy Aldehydes with Allyl- and Crotyltrifluorosilanes. Synthesis of <i>anti,anti</i>-Dipropionate Stereotriads and Stereodivergent Pathways for the Reactions with 2,3-<i>anti-</i> and 2,3-<i>syn</i>-α-Methyl-β-hydroxy Aldehydes
  作者：Sherry R. Chemler、William R. Roush

  DOI：10.1021/jo0267908

  日期：2003.2.1

  experiments performed with beta-hydroxy aldehydes 37a (anti) and the corresponding p-methoxybenzyl (PMB) ether 48, and between aldehyde 39 (syn) and the PMB ether 90, established that the 2,3-anti-beta-hydroxy aldehydes react predominantly through bicyclic transition states while the 2,3-syn aldehydes react predominantly through conventional Zimmerman-Traxler transition states. NMR studies established that

  描述了一种通过α-甲基-β-羟基醛与（Z）-巴豆基三氟硅烷（24）反应立体合成抗，反二丙酸酯立体三单元体的新方法。这些反应被设计为通过双环过渡态（例如31）发生，其中硅烷试剂与醛的β-羟基共价结合，巴豆基分子内转移。该方法用于合成锌卟啉的C（7）-C（16）区段（58），其中包含合成上具有挑战性的全抗立体五单元。令人惊讶地，2，3-抗-和2，3-syn-α-甲基-β-羟基醛以立体发散的方式与24：2，3-抗-β-羟基醛反应，得到目标的抗，抗二丙酸酯加合物具有高选择性，但是2的反应 3-syn-β-羟基醛的选择性较差。在与烯丙基-（68）和（E）-巴豆基三氟硅烷（27）的反应中，还显示出2,3-顺式对2,3-反-α-甲基-β-羟基醛的立体发散行为。用β-羟基醛37a（抗）和相应的对甲氧基苄基（PMB）醚48以及醛39（syn）和PMB醚90之间进行竞争实验，确定了2,3-抗β-羟基醛主要通过双环过渡态进行反应，而2
• Modular Synthesis of the C9−C27 Degradation Product of Aflastatin A via Alkyne−Epoxide Cross-Couplings
  作者：Omar Robles、Frank E. McDonald

  DOI：10.1021/ol800659z

  日期：2008.5.1

  A modular approach to the synthesis of complex polyketide natural products is demonstrated for the synthesis of the C9-C27 degradation product from aflastatin A. The product of the cross-coupling of C23-C27 terminal alkyne with C17-C22 epoxide underwent functionalization of the resulting internal alkyne, which was then coupled similarly with C9-C16 epoxide. This synthesis concluded with regio- and

  证明了从复杂的聚酮化合物天然产物合成的模块化方法，用于从黄素抑素A合成C9-C27降解产物。C23-C27末端炔烃与C17-C22环氧化合物的交叉偶联产物经过官能化处理内部炔烃，然后将其与C9-C16环氧类似地偶联。该合成结束于将甲基区域内和立体选择性加成到内部炔烃上，然后进行立体选择性加氢硼化-氧化。
• Allylation of quinones with allyl(trifluoro)silanes: Direct synthesis of isoprenoid quinones
  作者：Emiko Hagiwara、Yasuo Hatanaka、Ken-ichi Gohda、Tamejiro Hiyama

  DOI：10.1016/0040-4039(95)00394-r

  日期：1995.4

  Allylation of a variety of quinones with allyl(trifluoro)silanes takes place with high regioselectivity in the presence of FeCl3·6H2O, giving allylquinones in good yields. This method was used to synthesize biologically active isoprenoid quinones such as plastoquinone-1 and vitamin K1.

  在FeCl 3 ·6H 2 O的存在下，各种醌与烯丙基（三氟）硅烷的烯丙基化反应具有很高的区域选择性，从而能以高收率得到烯丙基醌。该方法用于合成具有生物活性的类异戊二烯醌，如plastoquinone-1和维生素K 1。
• .gamma.-Selective cross-coupling reaction of allyltrifluorosilanes: a new approach to regiochemical control in allylic systems
  作者：Yasuo Hatanaka、Yasuo Ebina、Tamejiro Hiyama

  DOI：10.1021/ja00018a076

  日期：1991.8
• Intramolecular allylation of the azo group of 2-(allylsilyl)azobenzenes and its photocontrol
  作者：Masaki Yamamura、Naokazu Kano、Takayuki Kawashima

  DOI：10.1016/j.jorganchem.2006.08.045

  日期：2007.1

  Pentacoordinate allylsilanes bearing an azobenzene moiety were synthesized and their structures were elucidated. The reaction of allyldifluorosilane (E)-7a with BF3 center dot OEt2 did not proceed, but (E)-7a was allowed to react with a fluoride ion to give tetrafluorosilicate 8a via intramolecular allyl-migration from the silicon atom onto the azo group. Activation of both the nucleophilic and electrophilic parts by the Si center dot center dot center dot N interaction was found to be important for promotion of the allyl-migration reaction. The azobenzene moiety of the allylsilane was reversibly isomerized by photoirradiation. The (Z)-7a formed by photoirradiation of (E)-7a is in a tetracoordinate state in contrast to the (E)-7a, and it did not react with a fluoride ion at all under the conditions where (E)-7a reacted quantitatively. The reactivity was successfully controlled without changing any conditions other than the change of the coordination number of the silicon atom induced by photoirradiation. (c) 2006 Elsevier B.V. All rights reserved.