(8S,8aS)-8-hydroxyhexahydroindolizin-5(1H)-one | 282534-26-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (8S,8aS)-8-hydroxyhexahydroindolizin-5(1H)-one
• 英文别名: (8aS)-8-hydroxyhexahydroindolizin-5(1H)-one；(-)-(8S,8aS)-8-hydroxy-5-indolizidinone；(8S,8aS)-8-hydroxy-2,3,6,7,8,8a-hexahydro-1H-indolizin-5-one
• CAS: 282534-26-3
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: ZFWFXXUMCVXKSR-BQBZGAKWSA-N

物化性质

• 熔点：
  98-100 °C
• 沸点：
  325.1±31.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  11
• 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：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (8S,8aS)-8-hydroxyhexahydroindolizin-5(1H)-one 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 为溶剂， 反应 22.0h， 以88%的产率得到(-)-(8S,8aS)-8-hydroxyindolizidine
  参考文献：
  名称：

  Regio- and diastereocontrolled C–H insertion of chiral γ- and δ-lactam diazoacetates. Application to the asymmetric synthesis of (8S,8aS)-8-hydroxyindolizidine

  摘要：

  δ-和δ-内酰胺重氮乙酸酯在 Rh2(MPPIM)4 催化下发生高效的分子内 CâH 插入反应，具有极佳的区域选择性和顺式-非对映选择性，可提供对合成有用的双环内酰胺内酯。

  DOI：

  10.1039/b606436a
• 作为产物：
  描述：

  (2S)-N-苄氧羰基-2-吡咯烷甲醛 在 samarium diiodide 、 palladium 10% on activated carbon 、 水 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 16.0h， 生成 (8S,8aS)-8-hydroxyhexahydroindolizin-5(1H)-one
  参考文献：
  名称：

  SmI 2介导的α-氨基酸衍生物的偶联。（-）-Pumiliotoxin 251D和（±）-表喹酰胺的正式合成

  摘要：

  描述了由二碘化sa介导的环状和非环状α-氨基酸衍生物与丙烯酸甲酯之间的偶联。该方法构成了以简单的两步方式构建吲哚并立定，喹喔啉和哌啶体系的有力工具。从这些氨基酸衍生物经过两个或三个步骤，即可完成（-）-铝毒素251D和（±）-表喹酰胺的正式合成。

  DOI：

  10.1021/ol400903n

文献信息

• α,β-Unsaturated Diazoketones as Platforms in the Asymmetric Synthesis of Hydroxylated Alkaloids. Total Synthesis of 1-Deoxy-8,8a-diepicastanospermine and 1,6-Dideoxyepicastanospermine and Formal Synthesis of Pumiliotoxin 251D
  作者：Barbara Bernardim、Vagner D. Pinho、Antonio C. B. Burtoloso

  DOI：10.1021/jo301967w

  日期：2012.11.2

  A versatile and concise approach for the stereoselective synthesis of mono-, di-, and trihydroxylated indolizidines is presented in four to six steps from Cbz-prolinal and a diazophosphonate. The key steps involved a Wolff rearrangement, followed by a stereoselective dihydroxylation/epoxidation reaction, from an α,β-unsaturated diazoketone. The strategy also permits extension to the synthesis of many

  从Cbz-脯氨酸和重氮膦酸酯的四至六个步骤中提出了一种立体选择性合成单羟基，二羟基和三羟基吲哚并吡啶的通用且简洁的方法。关键步骤涉及沃尔夫夫重排，然后是来自α，β-不饱和重氮酮的立体选择性二羟基化/环氧化反应。该策略还允许扩展到许多天然羟基化的吲哚并立定生物碱的合成，如pumiliotoxin 251D的正式合成所证明的。
• Nonracemic Bicyclic Lactam Lactones via Regio- and <i>cis</i>-Diastereocontrolled C−H Insertion. Asymmetric Synthesis of (8<i>S</i>,8a<i>S</i>)-Octahydroindolizidin-8-ol and (1<i>S</i>,8a<i>S</i>)-Octahydroindolizidin-1-ol
  作者：Andrew G. H. Wee、Gao-Jun Fan、Hypolite M. Bayirinoba

  DOI：10.1021/jo901790g

  日期：2009.11.6

  The Rh-2(MPPIM)(4)-catalyzed intraniolecular C-H insertion reaction of (S)- and (R)-1-benzyl-5-(alpha-diazoacetoxy)piperidin-2-one and (S)-1-benzyl-4-(alpha-diazoacetoxy)pyrrolidin-2-one proceeds with high regioselectivity and cis-diastereoselectivity to give good yields of chiral nonracemic bicyclic lactam lactones (BLLs). For (S)- and (R)-1-benzyl-5-(alpha-diazoacetoxy)piperidin-2-one, the regio selectivity of the C-H insertion is catalyst-dependent; for example, (S)-1-benzyl-5-(alpha-diazoacetoxy)piperidin-2-one undergoes C-H insertion at C-6 preferentially when Rh-2(5S-MPPIM)(4) is used, but with Rh-2(5R-MPPIM)(4), C-H insertion occurs preferentially at C-4. This effect is not observed in the reaction of (S)-1-benzyl-4-(alpha-diazoacetoxy)pyrrolidin-2-one. The utility of the BLLs as chiral building blocks in alkaloid synthesis is exemplified by the synthesis of (8S,8aS)-octahydroindolizidin-8-ol and (1S,8aS)-octahydroindolizidin-1-ol.
• Facile Transformation of 2-Azetidinones to 2-Piperidones:  Application to the Synthesis of the Indolizidine Skeleton and (8<i>S</i>,8a<i>S</i>)-Perhydro-8-indolizinol
  作者：Hyeon Kyu Lee、Jong Soo Chun、Chwang Siek Pak

  DOI：10.1021/jo026817n

  日期：2003.3.1

  The highly functionalized bicyclic lactam 7 was prepared from diolefinic-2-piperidone 18 by the use of ruthenium-catalyzed RCM, and in turn, 18 was derived via a two-carbon addition process from readily accessible 4-olefinic-2-azetidinone 13. Bicyclic lactams 7 and 20 could serve as potentially valuable intermediates for the chiral synthesis of various hydroxylated indolizidine alkaloids as exemplified by the synthesis of (8S,8aS)-perhydro-8-indolizinol 19.
• SmI₂-Mediated Couplings of α-Amino Acid Derivatives. Formal Synthesis of (−)-Pumiliotoxin 251D and (±)-Epiquinamide
  作者：Vagner D. Pinho、David J. Procter、Antonio C. B. Burtoloso

  DOI：10.1021/ol400903n

  日期：2013.5.17

  by samarium diiodide, is described. The method constitutes a powerful tool to construct indolizidine, quinolizidine, and piperidine systems in a straightforward two-step fashion. The formal synthesis of (−)-pumiliotoxin 251D and (±)-epiquinamide is achieved after two or three steps from these amino acid derivatives.

  描述了由二碘化sa介导的环状和非环状α-氨基酸衍生物与丙烯酸甲酯之间的偶联。该方法构成了以简单的两步方式构建吲哚并立定，喹喔啉和哌啶体系的有力工具。从这些氨基酸衍生物经过两个或三个步骤，即可完成（-）-铝毒素251D和（±）-表喹酰胺的正式合成。
• Regio- and diastereocontrolled C–H insertion of chiral γ- and δ-lactam diazoacetates. Application to the asymmetric synthesis of (8S,8aS)-8-hydroxyindolizidine
  作者：Gao-jun Fan、Zhongyi Wang、Andrew G. H. Wee

  DOI：10.1039/b606436a

  日期：——

  γ- and δ-Lactam diazoacetates undergo efficient intramolecular C–H insertion catalyzed by Rh2(MPPIM)4 with excellent regioselectivity and cis-diastereoselectivity to provide synthetically useful bicyclic lactam lactones.

  δ-和δ-内酰胺重氮乙酸酯在 Rh2(MPPIM)4 催化下发生高效的分子内 CâH 插入反应，具有极佳的区域选择性和顺式-非对映选择性，可提供对合成有用的双环内酰胺内酯。