1-methylenespiro<5.5>undecan-8-one | 113163-18-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methylenespiro<5.5>undecan-8-one
• 英文别名: 7-methylenespiro<5.5>undecan-2-one；7-Methylidenespiro[5.5]undecan-2-one；11-methylidenespiro[5.5]undecan-4-one
• CAS: 113163-18-1
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: PNGSWWSALUWGAS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1,2-二甲撑环己烷 在 盐酸 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 10.5h， 生成 1-methylenespiro<5.5>undecan-8-one
  参考文献：
  名称：

  One-step spiroannulation using 1,2-bis(methylene)cycloalkane-magnesium reagents

  摘要：

  A one-step method for the synthesis of a wide variety of spirocyclic systems has been developed based on the reactions of bis-electrophiles with a series of new 1,3-diene-magnesium reagents, the magnesium complexes of 1,2-bis(methylene)cycloalkanes. The direct metalation of 1,2-bis(methylene)cycloalkanes with highly reactive magnesium in THF at ambient temperature generates the corresponding diene-magnesium reagents in high yields. Reactions of the diene-magnesium reagents with 1,n-dibromoalkanes produce a large number of spirocarbocycles containing an exocyclic double bond. The ring sizes of the accessible spiro compounds can be any combinations of four- to seven-membered rings. In most cases, the initially alkylated intermediates can be trapped by protonation, giving the corresponding bromo olefins. Significantly, treatment of the diene-magnesium reagents with bromoalkyl nitriles leads to a one-step synthesis of keto-functionalized spirocycles. The initial adduct is believed to be a Grignard reagent containing a cyano group. When a bromo nitrile containing a cyclic moiety is used as the bis-electrophile, the approach provides a direct access to dispiroenones.

  DOI：

  10.1021/jo00050a036

文献信息

• Organobis(cuprates): a new class of reagents and method for spiroannelation
  作者：Paul A. Wender、Alan W. White

  DOI：10.1021/ja00215a035

  日期：1988.3

  Reaction d'organobiscuprates avec des halogeno-3 cyclohexene- et -cyclopentene-2ones: obtention de cyclohexanones et cyclopentanones spiranes en position 3

  反应 d'organobiscuprates avec deshalo-3 cyclohexene-et-cyclopentene-2ones: 获得环己酮和环戊酮螺环在位置 3
• The magnesium complexes of 1,2-dimethylenecycloalkanes: a new method for a one-step spiroannelation
  作者：Heping Xiong、Reuben D. Rieke

  DOI：10.1016/s0040-4039(00)92361-x

  日期：1991.9

  Reactions of new dienemagnesium reagents prepared from highly reactive magnesium and 1,2-dimethylenecycloalkanes with 1,n-dibromoalkanes and bromoalkylnitriles provide a one-step method for the synthesis of commonly encountered spirocyclic systems.
• SPIROANNELATION VIA ORGANOBIS(CUPRATES): 9,9-DIMETHYLSPIRO[4.5]DECAN-7-ONE
  作者：Wender, Paul A.、White, Alan W.、McDonald, Frank E.

  DOI：10.15227/orgsyn.070.0204

  日期：——
• WENDER, PAUL A.;WHITE, ALAN W., J. AMER. CHEM. SOC., 110,(1988) N 7, 2218-2223
  作者：WENDER, PAUL A.、WHITE, ALAN W.

  DOI：——

  日期：——
• One-step spiroannulation using 1,2-bis(methylene)cycloalkane-magnesium reagents
  作者：Reuben D. Rieke、Heping Xiong

  DOI：10.1021/jo00050a036

  日期：1992.11

  A one-step method for the synthesis of a wide variety of spirocyclic systems has been developed based on the reactions of bis-electrophiles with a series of new 1,3-diene-magnesium reagents, the magnesium complexes of 1,2-bis(methylene)cycloalkanes. The direct metalation of 1,2-bis(methylene)cycloalkanes with highly reactive magnesium in THF at ambient temperature generates the corresponding diene-magnesium reagents in high yields. Reactions of the diene-magnesium reagents with 1,n-dibromoalkanes produce a large number of spirocarbocycles containing an exocyclic double bond. The ring sizes of the accessible spiro compounds can be any combinations of four- to seven-membered rings. In most cases, the initially alkylated intermediates can be trapped by protonation, giving the corresponding bromo olefins. Significantly, treatment of the diene-magnesium reagents with bromoalkyl nitriles leads to a one-step synthesis of keto-functionalized spirocycles. The initial adduct is believed to be a Grignard reagent containing a cyano group. When a bromo nitrile containing a cyclic moiety is used as the bis-electrophile, the approach provides a direct access to dispiroenones.