<(p-Methoxyphenoxy)methyl>triphenylphosphonium chloride | 142041-44-9

• 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: <(p-Methoxyphenoxy)methyl>triphenylphosphonium chloride
• 英文别名: ((p-methoxyphenoxy)methyl)triphenylphosphonium chloride；(p-Methoxyphenoxy)methyltriphenylphosphonium chloride；[(p-Methoxyphenoxy)methyl]triphenylphosphonium chloride；[(4-Methoxyphenoxy)methyl](triphenyl)phosphonium chloride；(4-methoxyphenoxy)methyl-triphenylphosphanium;chloride
• CAS: 142041-44-9
• 化学式: C₂₆H₂₄O₂P*Cl
• 分子量: 434.902
• InChiKey: VYRQUXCOIQFWFI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.03
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <(p-Methoxyphenoxy)methyl>triphenylphosphonium chloride 在 正丁基锂 、 cerium(III) chloride 、 叔丁基锂 、 乙烯基-锂 作用下， 以 四氢呋喃 、 正己烷 、 正戊烷 为溶剂， 反应 2.0h， 生成 (1S,2S,4R)-2-<(S)-3-(Methoxymethoxy)-1-cyclohexen-1-yl>-1-<(E)-2-(p-methoxyphenoxy)vinyl>-7,7-dimethyl-2-norbornanol
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058
• 作为产物：
  描述：

  对苯二甲醚 在 过氧化氢苯甲酰 、 五氯化磷 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 50.0h， 生成 <(p-Methoxyphenoxy)methyl>triphenylphosphonium chloride
  参考文献：
  名称：

  A means for stereocontrolled introduction of the C-2 oxygen substituent in functionalized cis-tricyclo[9.3.1.03,8]pentadecanones related to taxol

  摘要：

  Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

  DOI：

  10.1021/jo00076a058

文献信息

• Tandem Cope-Cope Rearrangements
  作者：Ronan Guevel、Leo A. Paquette

  DOI：10.1021/ja00084a019

  日期：1994.3

  The first examples of tandem Cope-Cope rearrangements have been identified. When (1R * ,4S * ,6R * )-1,6-divinylbicyclo[2.2.2]oct-2-ene (6) was rearranged thermally, smooth conversion to (1R * ,8aS * )-1,2,3,5,6,8a-hexahydro-1-vinylnaphthalene (8) occurred. The mechanistic course of this isomerization was established by deuterium substitution as in 6-d 1 and by placement of a methoxyl group as in 14

  已经确定了串联 Cope-Cope 重排的第一个例子。当 (1R * ,4S * ,6R * )-1,6-divinylbicyclo[2.2.2]oct-2-ene (6) 热重排时，平滑转化为 (1R * ,8aS * )-1,2,3 ,5,6,8a-hexahydro-1-vinylnaphthalene (8) 出现。这种异构化的机理过程是通过 6-d 1 中的氘取代和 14 中的甲氧基基团建立的。 这些标签在热活化后的相应产品中的特定定位构成了对操作的特别严格的测试两个 [3,3] 的 sigmatropic 位移串联
• Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof
  作者：Steven W. Elmore、Leo A. Paquette

  DOI：10.1021/jo00109a020

  日期：1995.2

  The possibility of realizing the predominant exo a-hydroxylation of camphor-related ketones is described. Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack. Following conversion to MOM derivatives, the acidity of the alpha-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents. The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol. Further, the stereogenic centers are introduced in their proper absolute configuration. The steric demands of the [3,3] sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.
• Synthetic studies on furanoheliangolides. Stereocontrolled construction of the oxygen-bridged tricyclic framework
  作者：Dearg S. Brown、Leo A. Paquette

  DOI：10.1021/jo00042a036

  日期：1992.7

  The heavily functionalized 6,9-epoxycyclodeca[b]furan-11-ones 34 and 37 have been prepared in 13 steps from 4-methyl-2-[(phenylmethoxy)methyl]furan. The key elements of the scheme include a high-pressure Diels-Alder cycloaddition to 1-cyanovinyl acetate, highly regioselective hydroboration, controlled stepwise oxidation to give keto aldehyde 20, and thermal oxy-Cope rearrangement of both 32 and 36b. The prior introduction of a phenylthio substituent provides for the accommodation of different levels of unsaturation at a more advanced stage of furanoheliangolide construction. While the present strategy is developed around a racemic model, the potential for adoption of enantioselective features is immediate. The overall stereocontrolled sequence provides a general and flexible entry into oxygen-bridged frameworks closely related to substructures occurring in many furan-type germacranolides.