6-methylidene-3(3H)-pyrrolizidinone | 132279-21-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯里西啶类
• 英文名称: 6-methylidene-3(3H)-pyrrolizidinone
• 英文别名: 6-methylenehexahydro-3H-pyrrolizin-3-one；6-methylidene-2,5,7,8-tetrahydro-1H-pyrrolizin-3-one
• CAS: 132279-21-1
• 化学式: C₈H₁₁NO
• 分子量: 137.181
• InChiKey: WLWRVASFCXBFKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5-羟甲基-2-吡咯酮 在 碘苯二乙酸 、 碘 、 sodium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 6.0h， 生成 6-methylidene-3(3H)-pyrrolizidinone
  参考文献：
  名称：

  通过伯烷氧基自由基的 β-断裂从 β-氨基醇合成生物碱类似物

  摘要：

  伯烷氧基的裂解通常是夺氢和其他竞争反应的次要过程。然而，当使用 β-氨基醇作为底物时，断裂以良好到极好的产率进行，并且没有观察到副反应。断裂可以与烯丙基化或烷基化反应相结合，以得到生物碱类似物和官能化的氮杂环。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200600720

文献信息

• Radical based annulations of iodo lactams
  作者：Spencer Knapp、Frank S Gibson、Yun H Choe

  DOI：10.1016/s0040-4039(00)97856-0

  日期：1990.1

  N-Alkylation of iodo lactams with reactive alkyl halides, or of the derived selenide lactams with less reactive alkyl halides, leads to substrates for free radical initiated cyclization to pyrrolizidinones and indolizidinones, e. g. 2 → 3. The first examples of iodide / vinyl bromide, selenide / aldehyde, and selenide / vinyl chloride radical cyclizations are described.

  碘代内酰胺与反应性烷基卤化物的N-烷基化，或衍生的硒代内酰胺与反应性较低烷基卤化物的N-烷基化，导致底物被自由基引发环化为吡咯烷二酮和吲哚并二酮，例如2 → 3。描述了碘化物/溴乙烯，硒化物/醛和硒化物/氯乙烯自由基环化的第一个实例。
• A [3+2] Annulation Procedure for the Synthesis of Bicyclic Methylenepyrrolidines
  作者：Masahiro Sadakane、Ruth Vahle、Kerstin Schierle、Doris Kolter、Eberhard Steckhan

  DOI：10.1055/s-1997-691

  日期：——

  Reactions between 2-chloromethyl-3-trimethylsilyl-1-propene 1 and N-acyliminium ions, which were generated in situ from α-methoxy or α-acetoxy amides 2, give allylic chlorides 3 in good yields and high stereoselectivities. The allylic chlorides 3 were further transformed to bicyclic methylenepyrrolidines 4 which are building blocks for pharmacologically interesting compounds.

  2-chloromethyl-3-trimethylsilyl-1-propene 1 与 N-acyliminium 离子（由δ-甲氧基或δ-乙酰氧基酰胺 2 原位生成）发生反应，生成烯丙基氯化物 3，产率高，立体选择性强。烯丙基氯化物 3 可进一步转化为双环亚甲基吡咯烷 4，后者是具有药理学意义的化合物的组成单元。
• Radical routes to indolizidines. Synthesis of (-)-slaframine
  作者：Spencer Knapp、Frank S. Gibson

  DOI：10.1021/jo00044a011

  日期：1992.8

  The synthesis of (-)-slaframine (5) was executed in 11 steps and 25% overall yield from resolved 3(S)-hydroxy-4-pentenamide (22). Two cyclization reactions were used to form the indolizidine skeleton and also to provide the necessary stereocontrol at C-8a and C-6 of the natural product. "Iodolactamization" of 22 gave selectively the cis-pyrrolidinone 21. Later in the synthesis, a silane-mediated radical cyclization of the phenylseleno lactam 33 gave selectively the 6-alpha-hydroxyindolizidinone 35a, an event predictable from model studies-such as 14c --> 15c. Replacement of hydroxy with azido and reduction of the lactam carbonyl gave "slaframine azide", 38, a stable and easily convertible immediate precursor to 5.
• Synthesis of Alkaloid Analogues from β-Amino Alcohols by β-Fragmentation of Primary Alkoxyl Radicals
  作者：Alicia Boto、Dácil Hernández、Rosendo Hernández、Adriana Montoya、Ernesto Suárez

  DOI：10.1002/ejoc.200600720

  日期：2007.1

  fragmentation of primary alkoxyl radicals is usually a minor process with respect to hydrogen abstraction and other competing reactions. However, when β-amino alcohols were used as substrates, the scission proceeded in good to excellent yields and no side reactions were observed. The fragmentation can be coupled with an allylation or alkylation reaction, to give alkaloid analogues and functionalized

  伯烷氧基的裂解通常是夺氢和其他竞争反应的次要过程。然而，当使用 β-氨基醇作为底物时，断裂以良好到极好的产率进行，并且没有观察到副反应。断裂可以与烯丙基化或烷基化反应相结合，以得到生物碱类似物和官能化的氮杂环。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)