Methyl 4-oxo-9-decenoate | 143888-43-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: Methyl 4-oxo-9-decenoate
• 英文别名: Methyl 4-oxodec-9-enoate
• CAS: 143888-43-1
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: HGLRWHJZGDLVGV-UHFFFAOYSA-N

物化性质

• 沸点：
  294.5±23.0 °C(Predicted)
• 密度：
  0.963±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 4-oxo-9-decenoate 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 反应 6.0h， 生成 Decahydro-7H-4a,8-oxybenzocyclohepten-7-one
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions

  摘要：

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.

  DOI：

  10.1021/jo00047a032
• 作为产物：
  描述：

  6-溴-1-己烯 、 丁二酸单甲酯酰氯 生成 Methyl 4-oxo-9-decenoate
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions

  摘要：

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.

  DOI：

  10.1021/jo00047a032

文献信息

• Development of a Chiral N-Alkoxyamide Strategy and Application to the Asymmetric Total Synthesis of Fasicularin
  作者：Takaaki Sato、Ryo Minamikawa、Keisuke Fukaya、Akihiro Kobayashi、Yukinori Komiya、Shio Yamamoto、Daisuke Urabe、Noritaka Chida

  DOI：10.1055/a-1561-7815

  日期：2021.12

  The asymmetric total synthesis of fasicularin by a chiral N-alkoxyamide strategy is reported. Incorporation of the chiral alkoxy group onto an amide nitrogen changes the original reactivity of the amide, enabling two key transformations: aza-spirocyclization and the reductive Strecker reaction. DFT calculations indicate that pyramidalization of the N-alkoxyamide nitrogen is crucial to produce a cyclic

  报道了通过手性 N-烷氧基酰胺策略不对称全合成 fasicularin。将手性烷氧基结合到酰胺氮上会改变酰胺的​​原始反应性，从而实现两个关键转化：氮杂-螺环化和还原性 Strecker 反应。DFT 计算表明 N-烷氧基酰胺氮的锥体化对于产生平衡的环状半胺醛至关重要，该半胺醛经历氮杂-螺环化。手性烷氧基也用作立体控制元素以建立两个连续的立体中心。N-烷氧基内酰胺的铱催化还原 Strecker 反应为氨基腈提供了高非对映选择性。
• Asymmetric Total Synthesis of Fasicularin by Chiral <i>N</i>-Alkoxyamide Strategy
  作者：Shio Yamamoto、Yukinori Komiya、Akihiro Kobayashi、Ryo Minamikawa、Takeshi Oishi、Takaaki Sato、Noritaka Chida

  DOI：10.1021/acs.orglett.9b00478

  日期：2019.3.15

  The asymmetric total synthesis of fasicularin is reported. The key to success is the use of a chiral N-alkoxyamide to control both reactivity and stereoselectivity. This functional group enables the aza-spirocyclization and the reductive Strecker reaction, which cannot be realized with an ordinary amide. In addition, use of the chiral alkoxy group establishes two consecutive stereocenters in the aza-spirocyclization

  据报道法索贝林的不对称全合成。成功的关键是使用手性N-烷氧基酰胺控制反应性和立体选择性。该官能团能够实现氮杂-螺环化和还原性斯特雷克反应，这是普通酰胺无法实现的。另外，使用手性烷氧基通过远程立体控制在氮杂螺环化中建立两个连续的立体中心。
• Samarium(II) iodide-induced cascade reaction for tricyclic γ-lactone synthesis from acyclic keto diesters
  作者：Atsushi Kishida、Hiroto Nagaoka

  DOI：10.1016/j.tetlet.2008.08.105

  日期：2008.11

  Cascade reaction involving reductive cyclization, Dieckmann condensation, and lactonization of E- and Z-dimethyl 2-methyl-8-oxoundec-2-enedioates and Z-dimethyl 2-methyl-7-oxodec-2-enedioate with samarium(II) iodide was found to stereospecifically produce cis and trans bicyclo[4.4.0]decane (decalin) ring systems and trans bicyclo[4.3.0]nonan (perhydroindane) ring system each consisting of γ-lactone

  级联反应涉及碘化sa（II）的还原环化，狄克曼缩合和E-和Z-二甲基2-甲基-8-氧杂二-2-烯二酸酯和Z-二甲基2-甲基-7-氧杂-2-烯二酸酯的内酯化据发现，β-内酰胺可立体定向地产生分别由γ-内酯组成的顺式和反式双环[4.4.0]癸烷（十氢化萘）环系统和反式双环[4.3.0]壬南（全氢茚满）环系统。