(Z)-4-(dimethylphenylsilyl)-1-(phenylmethoxy)-3-buten-2-ol | 220496-89-9

• 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: (Z)-4-(dimethylphenylsilyl)-1-(phenylmethoxy)-3-buten-2-ol
• 英文别名: (Z)-4-[dimethyl(phenyl)silyl]-1-phenylmethoxybut-3-en-2-ol
• CAS: 220496-89-9
• 化学式: C₁₉H₂₄O₂Si
• 分子量: 312.484
• InChiKey: NQOQETJUYVCWSQ-YPKPFQOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-4-(dimethylphenylsilyl)-1-(phenylmethoxy)-3-buten-2-ol 在 光气 、 L-Selectride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 8.0h， 生成 rel-(2R,3R,3aR,4R,6R)-4-benzyloxy-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]-2-[(1R)-2-(phenylmethoxy)-1-(hydroxy)ethyl]hexahydroisoxazolo-[1,7b][1,2]oxazine
  参考文献：
  名称：

  Synthesis of (−)-7-Epiaustraline and (−)-1-Epicastanospermine

  摘要：

  Highly efficient and selective syntheses of the title compounds are described. The cornerstone of the synthetic plan is the tandem inter [4 + 2]/inter [3 + 2] cycloaddition process. These syntheses differ from previous applications of this strategy in that they incorporate an alkylation in the hydrogenolysis step to close the second ring of the azabicyclic systems. Notable features of the sequence are (1) the highly regio- and stereoselective [3 + 2] cycloaddition of nitronate 15 with siloxymethyl (Z)-beta-silylvinyl ketone (Z)-22b and (2) the highly selective reduction of the resulting ketone 24a with L-Selectride. A single-crystal X-ray structure analysis of synthetic (-)-7-epiaustraline confirmed that the targeted structure was successfully synthesized. This stimulated a reexamination of the structural assignment of the natural product. (-)-1-Epicastanospermine was synthesized in four steps from the common intermediate 27a. The absolute configuration of (-)-1-epicastanospermine was assured by single-crystal X-ray structure analysis of intermediate (-)-27a. Thus, the sign of the optical rotation had to be revised. The overall efficiency of these syntheses were 9 steps and 23% yield for (-)-7-epiaustraline and 10 steps and 20% yield for (-)-1-epicastanospermine.

  DOI：

  10.1021/jo991990d
• 作为产物：
  描述：

  顺-1,4-二苄氧基-2-丁烯 在 palladium on activated charcoal 喹啉 、 乙基溴化镁 、 氢气 、 臭氧 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 5.2h， 生成 (Z)-4-(dimethylphenylsilyl)-1-(phenylmethoxy)-3-buten-2-ol
  参考文献：
  名称：

  硝基烯烃的串联环加成化学：环硝酸盐的[3 + 2]环加成的立体化学过程的制备和理论研究。

  摘要：

  研究了两个环状硝酸酯与一系列偶极亲和剂之间的分子间[3 + 2]环加成反应。在所有情况下均观察到较高的面部选择性，并通过从头算过渡结构计算进行分析。单取代的双极性亲和剂与独家区域控制反应。双取代的亲油性与不同程度的区域控制反应，这取决于取代基。讨论了预测区域选择性的理论方法。由于空间效应，通常优选Exo选择性，并且对于顺式-二取代的双亲性试剂尤其如此。

  DOI：

  10.1021/jo9818374

文献信息

• Tandem Cycloaddition Chemistry of Nitroalkenes:  Preparative and Theoretical Studies on the Stereochemical Course of [3 + 2] Cycloaddition of Cyclic Nitronates
  作者：Scott E. Denmark、Mark Seierstad、B. Herbert

  DOI：10.1021/jo9818374

  日期：1999.2.1

  Intermolecular [3 + 2] cycloadditions between two cyclic nitronates and a series of dipolarophiles are examined. High facial selectivity is observed in all cases and is analyzed with the aid of ab initio transition structure calculations. Monosubstituted dipolarophiles reacted with exclusive regiocontrol. Disubstituted dipolarophiles reacted with varying degrees of regiocontrol, which was dependent

  研究了两个环状硝酸酯与一系列偶极亲和剂之间的分子间[3 + 2]环加成反应。在所有情况下均观察到较高的面部选择性，并通过从头算过渡结构计算进行分析。单取代的双极性亲和剂与独家区域控制反应。双取代的亲油性与不同程度的区域控制反应，这取决于取代基。讨论了预测区域选择性的理论方法。由于空间效应，通常优选Exo选择性，并且对于顺式-二取代的双亲性试剂尤其如此。
• Synthesis of (−)-7-Epiaustraline and (−)-1-Epicastanospermine
  作者：Scott E. Denmark、B. Herbert

  DOI：10.1021/jo991990d

  日期：2000.5.1

  Highly efficient and selective syntheses of the title compounds are described. The cornerstone of the synthetic plan is the tandem inter [4 + 2]/inter [3 + 2] cycloaddition process. These syntheses differ from previous applications of this strategy in that they incorporate an alkylation in the hydrogenolysis step to close the second ring of the azabicyclic systems. Notable features of the sequence are (1) the highly regio- and stereoselective [3 + 2] cycloaddition of nitronate 15 with siloxymethyl (Z)-beta-silylvinyl ketone (Z)-22b and (2) the highly selective reduction of the resulting ketone 24a with L-Selectride. A single-crystal X-ray structure analysis of synthetic (-)-7-epiaustraline confirmed that the targeted structure was successfully synthesized. This stimulated a reexamination of the structural assignment of the natural product. (-)-1-Epicastanospermine was synthesized in four steps from the common intermediate 27a. The absolute configuration of (-)-1-epicastanospermine was assured by single-crystal X-ray structure analysis of intermediate (-)-27a. Thus, the sign of the optical rotation had to be revised. The overall efficiency of these syntheses were 9 steps and 23% yield for (-)-7-epiaustraline and 10 steps and 20% yield for (-)-1-epicastanospermine.