1-methyl-3-oxo-hexahydropyrrolizine | 112924-38-6

• 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: 1-methyl-3-oxo-hexahydropyrrolizine
• 英文别名: (1S,8S)-1-methyl-1,2,5,6,7,8-hexahydropyrrolizin-3-one
• CAS: 112924-38-6
• 化学式: C₈H₁₃NO
• 分子量: 139.197
• InChiKey: XTFBZBQZGKHCEZ-BQBZGAKWSA-N

物化性质

• 沸点：
  243.3±7.0 °C(predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-methyl-3-oxo-hexahydropyrrolizine 在 lithium aluminium tetrahydride 作用下， 以87%的产率得到(-)-heliotridane
  参考文献：
  名称：

  通过手性吡咯烷重氮乙乙酰胺的高度非对映选择性和区域选择性催化碳氢插入反应合成吡咯嗪核苷碱

  摘要：

  吡咯烷酮，（1S，8S）-1-羟基吡咯烷并-3-酮和（-）-螺三tri烷，是由二取代的吡啶鎓（Ⅱ）四氢[Ⅱ]催化的碳氢插入，由2-取代的吡咯烷的重氮乙酰胺高产率制备的。 1-酰基咪唑烷基-2-一-4（S）-羧酸盐]。

  DOI：

  10.1016/0040-4039(96)00056-1
• 作为产物：
  描述：

  L-脯氨醇 在 镍 氢氧化钾 、 sodium hydroxide 、 N-氯代丁二酰亚胺 、 pyridine-SO3 complex 、 偶氮二异丁腈 、 三正丁基氢锡 、 一水合肼 、 三乙胺 作用下， 以 四氯化碳 、 乙醚 、 乙醇 、 二氯甲烷 、 乙二醇 、 二甲基亚砜 、 苯 为溶剂， 反应 33.0h， 生成 1-methyl-3-oxo-hexahydropyrrolizine
  参考文献：
  名称：

  Carbamoylmethyl Radical Cyclization: Formal Synthesis of (-)-Trachelanthamidine.

  摘要：

  三丁基氢化锡介导的 (2S)-N-(α-氯乙酰基)-2-乙烯基吡咯烷 13a, b 和 15 与来自 (S)-prolinol 的双(苯硫基)乙酰同系物-14 的自由基环化反应，以高区域和非对映选择性的方式得到了 (1R, 7aS)-hexahyrdo1-methyl-3H-pyrrolizin-3-one (17) 及其衍生物 16a, b。这种自由基环化方法成功地应用于 (-)-trachelanthamidine 的正式全合成。

  DOI：

  10.1248/cpb.40.2308

文献信息

• New Entry to γ-Butyrolactams by Free Radical Cyclization of<i>N</i>-Allyl-α-chloro-α-(methylthio)acetamides. Formal Total Synthesis of (±)-Pseudoheliotridane
  作者：Hiroyuki Ishibashi、Tatsunori Sato、Maki Irie、Suzumi Harada、Masazumi Ikeda

  DOI：10.1246/cl.1987.795

  日期：1987.5.5

  Tributyltin hydride-azobisisobutyronitrile induced radical cyclization of N-allyl-α-chloro-α-(methylthio)acetamides afforded γ-butyrolactams. This method was applied to the formal total synthesis of (±)-pseudoheliotridane.

  三丁基氢化锡-偶氮二异丁腈诱导 N-烯丙基-α-氯-α-（甲硫基）乙酰胺的自由基环化，得到 γ-丁内酰胺。将该方法应用于(±)-pseudoheliotridane的正式全合成。
• Synthesis of the alkaloids (−)-heliotridane and (−)-isoretronecanol via π-allyltricarbonyliron lactam complexes.
  作者：Julian G. Knight、Steven V. Ley

  DOI：10.1016/0040-4039(91)85056-b

  日期：1991.11

  A novel synthesis of the pyrrolizidine alkaloids (−)-heliotridane (1) and (−)-isoretronecanol (2) is described. The key steps involve the conversion of a proline-derived carbamate (10) into the π-allyltricarbonyliron lactam complex (4) and the exhaustive carbonylation of this to give the pivotal intermediate γ-lactam (3). Lactam (3) has been converted into the title compounds by standard methods.

  描述了吡咯烷核生物碱（-）-三碘三环烷（1）和（-）-异戊烯醇（2）的新型合成方法。关键步骤包括将脯氨酸衍生的氨基甲酸酯（10）转化为π-烯丙基三羰基铁内酰胺复合物（4）并对其进行彻底的羰基化，以得到关键的中间体γ-内酰胺（3）。内酰胺（3）已通过标准方法转化为标题化合物。
• Ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic .alpha.-chloro-.alpha.-thioacetamides. Synthesis of (-)-trachelanthamidine and formal total synthesis of (.+-.)-haemanthidine and (.+-.)-pretazettine
  作者：Hiroyuki Ishibashi、Nahoko Uemura、Hiroshi Nakatani、Mika Okazaki、Tatsunori Sato、Nobuyuki Nakamura、Masazumi Ikeda

  DOI：10.1021/jo00061a005

  日期：1993.4

  A new method for the synthesis of five-membered lactams by ruthenium-catalyzed chlorine atom transfer cyclizations of N-allylic alpha-chloro-alpha-thioacetamides and the application of the method to the synthesis of the title alkaloids are described. A benzene solution of N-allyl-N-methyl-alpha-chloro-alpha-(phenylthio)acetamide (6) was heated at 140-degrees-C in the presence of RuCl2(PPh3)3 to give alpha-thio-beta-(chloromethyl)-substituted gamma-lactam 8 as a mixture of cis and trans isomers in a ratio of ca. 3:7. NH congener 11, however, gave no cyclization product. Heating chloro sulfides 18 and 19, prepared from L-prolinol, with RuCl2(PPh3)3 afforded bicyclic lactams 20 and 21, respectively. Treatment of 20 with cesium propanoate gave predominantly cyclopropane derivative 25, whereas S-methyl congener 21 provided esters 24 in good yield. Desulfurization of 24 with Raney nickel followed by reduction with LiAlH4 furnished (-)-trachelanthamidine (28). On the other hand, N-(cyclohex-2-en-1-yl) derivative 30, when heated with RuCl2(PPh3)3, afforded octahydroindol-2-ones 31a,b. The formation of 31a,b indicated that the intramolecular addition of the chloro sulfide of 30 to the olefinic bond proceeded in an anti-mode. By contrast, 2-phenyl-substituted derivative 38 gave syn-addition product 39. The difference between the modes of cyclization of 30 and 38 can be explained by assuming the intermediacy of radical 34. When R = H, the chlorine atom attacks the convex face of the fused bicyclic system of 34 to lead to 31a,b, whereas the steric bulk of the angular phenyl group (R = Ph) is apparently sufficient to direct the chlorine atom to the concave face. Heating chloro sulfide 48, prepared in a highly stereocontrolled manner from cyclohexene 42, with RuCl2(PPh3)3 afforded bicyclic lactam 49. Oxidation of 49 with m-CPBA followed by Pummerer rearrangement/hydrolysis gave keto lactam 51, which was dehydrochlorinated with DBU to give olefin 52. LiAlH4 reduction of 52 and acylation with pivaloyl chloride provided ester 54, a key intermediate in Martin's total synthesis of (+/-)-haemanthidine (41) and (+/-)-pretazettine (40).
• New synthesis of heterocycles by use of palladium catalyzed cycli zation of α-haloamide with internal double bond
  作者：Miwako Mori、Nana Kanda、Izumi Oda、Yoshio Ban

  DOI：10.1016/s0040-4020(01)91346-8

  日期：1985.1
• Ikeda, Masazumi; Teranishi, Hirotaka; Nozaki, Kohei, Journal of the Chemical Society. Perkin transactions I, 1998, # 10, p. 1691 - 1697
  作者：Ikeda, Masazumi、Teranishi, Hirotaka、Nozaki, Kohei、Ishibashi, Hiroyuki

  DOI：——

  日期：——