trimethyl-[(E)-4-(4-methylphenyl)sulfonyl-5-phenylpent-3-enyl]silane | 210572-73-9

• 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: trimethyl-[(E)-4-(4-methylphenyl)sulfonyl-5-phenylpent-3-enyl]silane
• CAS: 210572-73-9
• 化学式: C₂₁H₂₈O₂SSi
• 分子量: 372.604
• InChiKey: MGQJHFMBJIBCAD-SRZZPIQSSA-N

物化性质

• 沸点：
  519.7±50.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.62
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trimethyl-[(E)-4-(4-methylphenyl)sulfonyl-5-phenylpent-3-enyl]silane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 以63%的产率得到(E)-penta-2,4-dien-1-ylbenzene
  参考文献：
  名称：

  (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

  摘要：

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.

  DOI：

  10.1021/jo970546c
• 作为产物：
  描述：

  3-丁烯基三甲基硅烷 在 六甲基磷酰三胺 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 29.17h， 生成 trimethyl-[(E)-4-(4-methylphenyl)sulfonyl-5-phenylpent-3-enyl]silane
  参考文献：
  名称：

  (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

  摘要：

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.

  DOI：

  10.1021/jo970546c

文献信息

• (<i>E</i>)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-1-butene:  An Advantageous Synthetic Equivalent for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion
  作者：Timothy P. Meagher、Harold Shechter

  DOI：10.1021/jo970546c

  日期：1998.6.1

  The (E)-1-(arylsulfonyl)-4-(trimethylsilyl)-1-butenes 9, 25, and 26 are prepared by CuCl2-promoted and by photolytic additions of their precursor l-arylsulfonyl chlorides and bromides to 4-(trimethylsilyl)-1-butene (14) and then dehydrohalogenation of the resulting 1-(arylsulfonyl)-2-halo-4-(trimethylsilyl)butanes 15a, 15b, 23a, and 23b with KOH, LDA, or n-BuLi. Silylbutene 14 is obtained from reaction of [(trimethylsilyl)methyl]magnesium chloride (16, X = Cl) and allyl bromide (17) and better by protiodesilylations of (E)- and (Z)-1,4-bis(trimethylsilyl)-2-butenes (20) with sulfuric or trifluoroacetic acids. (Arylsulfonyl)(trimethylsilyl)-1-butenes 9, 25, and 26 are converted efficiently by LDA or n-BuLi at -78 degrees C to 1-(arylsulfonyl)-1-lithio-4-(trimethylsilyl)-1-butenes 10, 27a, and 27b, respectively. Reactions of 27a and 27b with deuterium oxide yield (E)-1-(4-chlorophenylsulfonyl)-1-deuterio-4-(trimethylsilyl)-1-butene (28a, 83%) and (E)-1-deuterio-1-(4-methylphenylsulfonyl)-4-(trimethylsilyl) 1-butene(28b, 89%), respectively. 1-Lithio derivatives 10, 27a, and 27b undergo benzylations by benzyl bromide in THF/HMPA with retention of the positions of their olefinic double bonds to give the (E)-2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-2-pentenes 29a, 29b, and 29c, respectively, in 84-90% yields. Of particular interest is that asa-care isomerized to their corresponding 2-(arylsulfonyl)-1-phenyl-5-(trimethylsilyl)-3-pentenes 30a-c, respectively, which then undergo conjugative eliminations df their arylsulfonyl and their trimethylsilyl groups to give (E)-5-phenyl-1,3-pentadiene (33) in 56-63% yields upon reactions with TBAF in THF at 25 degrees C. Further, 27b reacts with 1,3-dichloropropane to form 1-chloro-4-(4-methylphenylsulfonyl)-7-(trimethylsilyl)-4-heptene (35) which is cyclized by n-BuLi to 1-(4-methylphenylsulfonyl)-l-(3-(trimethylsilyl)-1-propenyl) (37, 67%). Elimination of 37 by TBAF then gives allylenecyclobutane (34, n = 3, 84%) simply. This study thus reveals that 8, 25, and 26 have outstanding potential as 1-(1,3-butadienyl) anion (7) and 1,1-(1,3-butadienyl) dianion (8) synthons.