1-Methyl-2-trimethylsilylethylidenetriphenylphosphorane | 63922-70-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-Methyl-2-trimethylsilylethylidenetriphenylphosphorane
• 英文别名: Phosphorane, [1-methyl-2-(trimethylsilyl)ethylidene]triphenyl-；triphenyl(1-trimethylsilylpropan-2-ylidene)-λ5-phosphane
• CAS: 63922-70-3
• 化学式: C₂₄H₂₉PSi
• 分子量: 376.554
• InChiKey: DRFWLJVPGVUWRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-Methyl-2-trimethylsilylethylidenetriphenylphosphorane 在 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 33.33h， 生成 1-methoxy-6-methyl-8-(trimethylsilyl)-(E,Z)-1,6-octadiene
  参考文献：
  名称：

  Intramolecular anodic olefin coupling reactions: a useful method for carbon-carbon bond formation

  摘要：

  The utility of intramolecular anodic olefin coupling reactions for effecting carbon-carbon bond formation has been examined. All of the successful cyclizations studied utilized either an alkyl or silyl enol ether as one of the participating olefins. The enol ethers could be coupled to simple alkyl olefins, styrenes, and allylsilanes in isolated yields ranging from 57 to 84%. The reactions were found to be effective for generating both five- and six-membered rings. The best conditions for cyclization utilized a reticulated vitreous carbon anode, constant-current conditions in an undivided cell, and a lithium perchlorate in either 50% methanol/tetrahydrofuran or 20% methanol/dichloromethane electrolyte solution. The use of an allylsilane as one of the participating olefins allowed for the regiospecific formation of olefinic products. In addition to the olefinic products, these reactions produced a small amount of a cyclized ether product in which the silyl group had not been eliminated. Deuterium-labeling studies showed that at least half of this ether byproduct arose from intramolecular migration of the methoxy group that was initially part of the starting enol ether to the carbon-beta to the silyl group. Intramolecular migration reactions of this type were found to participate in a number of the reported cyclization reactions.

  DOI：

  10.1021/ja00019a038
• 作为产物：
  描述：

  碘甲基三甲基硅烷 、 乙基三苯基溴化膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.75h， 生成 1-Methyl-2-trimethylsilylethylidenetriphenylphosphorane
  参考文献：
  名称：

  酯烯醇化物的有效氧化自由基环化，以碳正硅烷基化为终止：环戊烷单萜和类似物的合成。

  摘要：

  [反应：见正文]已开发出一种有效的氧化自由基环化方法，用于由可循环SET氧化剂六氟磷酸二铯铁诱导的ω-甲硅烷基烯丙基酯烯酸酯合成2-烯基环戊烷或环己烷羧酸酯。一种新的串联烷氧基羰基化/氧化自由基环化/阳离子终止方法为环戊烷单萜二氢荆芥内酯和类似物的五步合成奠定了基础。

  DOI：

  10.1021/ol036233n

文献信息

• Syn-diastereoselective alkenylation with a modified Seyferth–Wittig reagent: modification of the silyl substituents and isopropenylation
  作者：Masamitsu Tsukamoto、Hideo Lio、Takashi Tokoroyama

  DOI：10.1039/c39860000880

  日期：——

  The introduction of electronegative substituents onto the silyl group of triaryl(2-silylethylidene)phosphorane promotes eliminative silyl migration relative to the Wittig reaction; the combination of this effect with modification of the phosphorane substituents leads to highly diastereoselective reagents for alkenylation.

  相对于Wittig反应，在三芳基（2-甲硅烷基亚乙基）膦烷的甲硅烷基上引入负电取代基可促进消除甲硅烷基的迁移。这种作用与磷烷取代基修饰的结合产生了高度非对映选择性的烯基化试剂。
• Total synthesis of (±)-α-allokainic acid via two allylsilane N-acyliminium ion reactions
  作者：Hendrik H Mooiweer、Henk Hiemstra、W.Nico Speckamp

  DOI：10.1016/s0040-4020(01)86407-3

  日期：1991.1

  A total synthesis of racemic α-allokainic acid is described, which starts from allylsilane 8 and methoxy- or chloroglycine derivative 9, and proceeds fully stereoselectively in nine steps and 1.1% overall yield. Key steps are the intermolecular N-acyliminium ion coupling of 8 with 9 and an intramolecular allylsilane N-acyliminium ion reaction of 4, which closes the pyrrolidine ring by C4-C5 bond formation

  描述了外消旋α-链烷酸的全合成，其从烯丙基硅烷8和甲氧基或氯甘氨酸衍生物9开始，并且以九个步骤完全立体选择性地进行，总产率为1.1％。关键步骤是分子间Ñ -acyliminium离子的耦合8与9和分子内烯丙基硅烷Ñ -acyliminium离子反应的4，封闭由C4-C5键形成吡咯烷环。值得注意的是，为了制备δ-内酯5，将8与9偶联的分子内变体未能进行。
• A multistep rearrangement from 2,2-disubstituted-1,3-cyclohexanediones to 3-substituted 2-cyclohexenones via phosphonate anions and its application to a formal synthesis of (.+-.)-.alpha.-acoradiene
  作者：Yoshinori Yamamoto、Toshiaki Furuta

  DOI：10.1021/jo00300a003

  日期：1990.6
• Unusual reaction of 2-trimethylsilylethylidenetriarylphosphoranes (seyferth-wittig reagent) with α-methylaldehydes: a novel method for highly cram-diastereoselective addition of vinyl anion equivalent
  作者：Masamitsu Tsukamoto、Hideo Iio、Takashi Tokoroyama

  DOI：10.1016/s0040-4039(00)88933-9

  日期：1985.1
• A general route to terminally substituted allylic derivatives of silicon and tin. Preparation of allylic lithium reagents
  作者：Dietmar Seyferth、Karl R. Wursthorn、Robert E. Mammarella

  DOI：10.1021/jo00438a037

  日期：1977.9