2-(1-Oxo-5-hexen-1-yl)-1-<2-(trimethylsilyl)ethynyl>benzene | 166757-19-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(1-Oxo-5-hexen-1-yl)-1-<2-(trimethylsilyl)ethynyl>benzene
• 英文别名: 1-[2-(2-Trimethylsilylethynyl)phenyl]hex-5-en-1-one
• CAS: 166757-19-3
• 化学式: C₁₇H₂₂OSi
• 分子量: 270.447
• InChiKey: XSBUXJKRPKPKRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.45
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(1-Oxo-5-hexen-1-yl)-1-<2-(trimethylsilyl)ethynyl>benzene 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 40.0h， 生成 Methyl 2-<2-<2-(1-oxo-5-hexenyl)phenyl>ethynyl>benzoate
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047
• 作为产物：
  描述：

  2-[(三甲基硅基)乙炔基]苯甲醛 在 magnesium 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 2-(1-Oxo-5-hexen-1-yl)-1-<2-(trimethylsilyl)ethynyl>benzene
  参考文献：
  名称：

  An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond

  摘要：

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.

  DOI：

  10.1021/jo00122a047

文献信息

• An Efficient Gold-Catalyzed Domino Process for the Construction of Tetracyclic Ketoethers
  作者：Tobias Groß、Peter Metz

  DOI：10.1002/chem.201302985

  日期：2013.10.25

  Au, yeah! Catalytic amounts of gold(III)chloride allow a mild and efficient oxidative domino cyclization/cycloaddition of enyne carbonyl compounds 1 and 4 to give the tetracycles 2 or 5, respectively, in the presence of pyridine N‐oxide 3 (see scheme; DCE = 1,2‐dichloroethane).

  哦，是的！在吡啶N-氧化物3存在下，催化量的氯化金（III）可以温和有效地氧化烯炔羰基化合物1和4进行氧化多米诺环化/环加成，分别生成四环2或5（参见方案; DCE = 1,2-二氯乙烷）。
• An Unusual Example of a 6-Endo-Dig Addition to an Unactivated Carbon-Carbon Triple Bond
  作者：Albert Padwa、Keith E. Krumpe、M. David Weingarten

  DOI：10.1021/jo00122a047

  日期：1995.9

  Methyl 2-[2-[2-(1-hydroxy-1-ethyl)phenyl]ethynyl]benzoate was prepared as an intermediate for subsequent conversion to an a-diazo ketone. Under the basic conditions used to hydrolyze the methyl ester, the neighboring hydroxyl functionality underwent reaction with the unactivated acetylenic group, producing a benzopyranyl-substituted alpha-diazoacetophenone. Treatment of this diazocarbonyl compound with a catalytic quantity of rhodium(II) mandelate afforded a novel dibenzo[a,e]cyclononenone derivative. The reaction proceeds via an initially formed oxonium ylide which rearranges further by means of a 1,2-alkyl shift. A prime factor in determining the direction of internal cyclization to the triple bond is the presence of the carbomethoxy group in the ortho position of the beta-phenyl ring. Thus, in contrast with related systems which exhibit a clear preference for 5-exo-dig cyclization at the acetylenic center, the 6-endo-dig addition is the preferred pathway for the o-formyl- and o-carbomethoxy-substituted alkynyl alcohols. Careful monitoring of the reaction actually showed that the reaction proceeds by initial formation of the 5-exo-dig product followed by a novel rearrangement to the 6-endo product.