(2S,3R,6R)-(-)-2-(3-hydroxypropyl)-3-methyl-6-(pent-4-enyl)piperidine | 142319-57-1

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (2S,3R,6R)-(-)-2-(3-hydroxypropyl)-3-methyl-6-(pent-4-enyl)piperidine
• 英文别名: 3-[(2S,3R,6R)-3-methyl-6-pent-4-enylpiperidin-2-yl]propan-1-ol
• CAS: 142319-57-1
• 化学式: C₁₄H₂₇NO
• 分子量: 225.374
• InChiKey: CSCYBTSYDQYCHD-MCIONIFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3R,6R)-(-)-2-(3-hydroxypropyl)-3-methyl-6-(pent-4-enyl)piperidine 在 三乙胺 、 三苯基膦 作用下， 以 四氯化碳 、 乙腈 为溶剂， 反应 32.0h， 以71%的产率得到(-)-indolizidine 207A
  参考文献：
  名称：

  Enantioselective Synthesis of the Dendrobatid Alkaloid (-)-Indolizidine 207A

  摘要：

  An enantioselective synthesis of the Dendrobates alkaloid (-)-indolizidine 207A (1) is reported. The key intermediate in this synthesis is alcohol 6 (Scheme 1), prepared in four steps from geraniol with control of both relative and absolute configuration.

  DOI：

  10.1021/jo00108a011
• 作为产物：
  描述：

  Methyl (4R)-4-methyl-5-hexenoate 在 palladium on activated charcoal 氢氧化钾 、 草酰氯 、 二甲基硫 、 tetrapropylammonium periodate 、 盐酸羟胺 、 氢气 、 碳酸氢钠 、 sodium carbonate 、 臭氧 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 氯仿 、 水 为溶剂， -65.0~25.0 ℃ 、101.33 kPa 条件下， 反应 45.5h， 生成 (2S,3R,6R)-(-)-2-(3-hydroxypropyl)-3-methyl-6-(pent-4-enyl)piperidine
  参考文献：
  名称：

  Enantiogenic total syntheses of (-)-indolizidines (bicyclic gephyrotoxins) 205A, 207A, 209B, and 235B via the intramolecular Diels-Alder reaction of a chiral N-acylnitroso compound

  摘要：

  A general protocol for the enantiogenic total syntheses of a series of the 5-substituted 8-methylindolizidine class of alkaloids from the arrow poison frog, i.e., (-)-indolizidines 205A (1), 207A (2), 209B (3), and 235B (4), is described, in which a key step is the asymmetric intramolecular Diels-Alder reaction of the chiral N-acylnitroso compound 8 leading to the bicyclic oxazinolactam 7 which was utilized as a versatile common chiral intermediate for the preparation of these alkaloids. Subsequent introduction of the C-5 (in future) side chain was elaborated by means of a completely stereocontrolled process involving a Grignard reaction followed by reduction with NaBH4 in acidic media. The bicyclic oxazines 20a, 24, and 26 thus obtained were then subjected to reductive N-O bond cleavage followed by cyclodehydration using PPh3/CBr4/Et3N, which provided the (-)-enantiomers of the title alkaloids.

  DOI：

  10.1021/jo00036a024

文献信息

• Highly stereoselective construction of trans(2,3)-cis(2,6)-trisubstituted piperidines: An application to the chiral synthesis of Dendrobates alkaloids
  作者：Naoki Toyooka、Keiko Tanaka、Takefumi Momose、John W Daly、H.Martin Garraffo

  DOI：10.1016/s0040-4020(97)00641-8

  日期：1997.7

  indolizidine and 1,4-disubstituted quinolizidine system found in Dendrobates alkaloids has been developed. The key step for this synthesis is the highly stereoselective Michael reaction of a didehydropiperidinecarboxylate (1) to afford a trans(2,3)-cis(2,6)-trisubstituted piperidine. In this manner, the chiral formal synthesis of indolizidines 207A and 209B and the total synthesis of indolizidines

  已开发出一种通向Dendrobates生物碱中的5,8-二取代的吲哚并立核苷和1,4-二取代的喹oli嗪系的通用且灵活的途径。该合成的关键步骤是二脱氢哌啶羧酸酯（1）的高度立体选择性迈克尔反应，得到反式（2,3）-顺式（2,6）-三取代哌啶。以这种方式，已经实现了吲哚并咪唑207A和209B的手性形式合成以及喹啉并咪唑207I的吲哚并咪唑223J，235B'和Cl-顶基的总合成。
• Asymmetric Synthesis of the Indolizidine Alkaloids 207A, 209B, and 235B': 6-Substituted 2,3-Didehydropiperidine-2-carboxylate as a Versatile Chiral Building Block
  作者：Takefumi Momose、Naoki Toyooka

  DOI：10.1021/jo00084a004

  日期：1994.3

  The asymmetric synthesis of 5-substituted 8-methylindolizidines 1-3 was,achieved via the highly stereocontrolled Michael reaction of the title compound 5.
• Enantiogenic total syntheses of (-)-indolizidines (bicyclic gephyrotoxins) 205A, 207A, 209B, and 235B via the intramolecular Diels-Alder reaction of a chiral N-acylnitroso compound
  作者：Yuji Shishido、Chihiro Kibayashi

  DOI：10.1021/jo00036a024

  日期：1992.5

  A general protocol for the enantiogenic total syntheses of a series of the 5-substituted 8-methylindolizidine class of alkaloids from the arrow poison frog, i.e., (-)-indolizidines 205A (1), 207A (2), 209B (3), and 235B (4), is described, in which a key step is the asymmetric intramolecular Diels-Alder reaction of the chiral N-acylnitroso compound 8 leading to the bicyclic oxazinolactam 7 which was utilized as a versatile common chiral intermediate for the preparation of these alkaloids. Subsequent introduction of the C-5 (in future) side chain was elaborated by means of a completely stereocontrolled process involving a Grignard reaction followed by reduction with NaBH4 in acidic media. The bicyclic oxazines 20a, 24, and 26 thus obtained were then subjected to reductive N-O bond cleavage followed by cyclodehydration using PPh3/CBr4/Et3N, which provided the (-)-enantiomers of the title alkaloids.
• Enantioselective Synthesis of the Dendrobatid Alkaloid (-)-Indolizidine 207A
  作者：Douglass F. Taber、Mohammad Rahimizadeh、Kamfia K. You

  DOI：10.1021/jo00108a011

  日期：1995.2

  An enantioselective synthesis of the Dendrobates alkaloid (-)-indolizidine 207A (1) is reported. The key intermediate in this synthesis is alcohol 6 (Scheme 1), prepared in four steps from geraniol with control of both relative and absolute configuration.