(S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯 | 143264-54-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯
• 英文名称: (S)-N-benzyloxycarbonyl-2-piperidineacetaldehyde
• 英文别名: (2S)-N-<(benzyloxy)carbonyl>-2-(formylmethyl)piperidine；Benzyl (2S)-2-(2-oxoethyl)piperidine-1-carboxylate
• CAS: 143264-54-4
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: FSPPNBAJRZTJGR-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  (S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯 在 氢氧化钾 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 5.33h， 生成 <11(2S)>-11-<2-piperidyl>>-9-undecenoic acid
  参考文献：
  名称：

  Enantioselective Total Synthesis of the Macrocyclic Spermidine Alkaloid (−)-Oncinotine

  摘要：

  The macrocyclic spermidine alkaloid (-)-oncinotine (1), isolated from Oncinotis nitida (Apocynaceae), was synthesized enantioselectively for the first time based on intramolecular iminium ion cyclization utilizing enantiomerically pure (2S)-N-[(benzyloxy)carbonyl]-2-piperidineacetaldehyde (8) as a chiral starting material. The required 8 was derived from the erythro adduct 16, which was obtained by diastereoselective 1,3-dipolar cycloaddition between 2,3,4,5-tetrahydropyridine 1-oxide (4) and (3S)-3-[(tert-butyldiphenylsilyl)oxy]-4-methyl-1-pentene (15). Wittig condensation of 8 with [8-(methoxycarbonyl)octyl]triphenylphosphonium iodide (21) followed by saponification provided the chiral piperidine moiety 23, which was coupled with the N-propyl-1,4-butanediamine segment 29 by using diethoxyphosphoryl cyanide in the presence of triethylamine to afford the tertiary amide 30. Conversion of 30 to the aldehyde 34 via desilylation and Swern oxidation, followed by hydrogenation over a palladium hydroxide catalyst under high dilution led to in situ formation of the transient iminium ion 35, which was further hydrogenated to form 33 in a single operation. Subsequent removal of the Boc protecting group resulted in (-)-oncinotine (1).

  DOI：

  10.1021/jo9518258
• 作为产物：
  描述：

  <2S,2(2R),2(3S)>-N-<(benzyloxy)carbonyl>-2-(2,3-dihydroxy-4-methylpentyl)piperidine 在 过碘酸 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 (S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯
  参考文献：
  名称：

  分子间硝酮环加成与手性烯丙基醚的非对面选择性。辛氨酸手性合成中的应用

  摘要：

  环硝酮与手性烯丙基醚的分子间环加成反应具有赤型选择性，其中达到的选择性程度取决于与烯丙基手性中心相连的烷基取代基的大小，这些反应适用于旋光活性的合成生物碱的甜菜碱。

  DOI：

  10.1016/0040-4039(92)80019-g

文献信息

• Diastereofacial selectivity in intermolecular nitrone cycloadditions to chiral allyl ethers. Application to Chiral Synthesis of Coniine
  作者：Masayuki Ito、Masae Maeda、Chihiro Kibayashi

  DOI：10.1016/0040-4039(92)80019-g

  日期：1992.6

  The intermolecular cycloadditions of a cyclic nitrone to chiral allyl ethers take place with erythro selectivity, where the degree of selectivity achieved is dependent upon the size of the alkyl substituent attached to the allylic chiral center, and these reactions are applied to the synthesis of optically active alkaloid coniine.

  环硝酮与手性烯丙基醚的分子间环加成反应具有赤型选择性，其中达到的选择性程度取决于与烯丙基手性中心相连的烷基取代基的大小，这些反应适用于旋光活性的合成生物碱的甜菜碱。
• Improved Protocol for Asymmetric, Intramolecular Heteroatom Michael Addition Using Organocatalysis: Enantioselective Syntheses of Homoproline, Pelletierine, and Homopipecolic Acid
  作者：Erik C. Carlson、Lauren K. Rathbone、Hua Yang、Nathan D. Collett、Rich G. Carter

  DOI：10.1021/jo800749t

  日期：2008.7.1

  indoline, and piperidine rings using an organocatalyzed, intramolecular heteroatom Michael addition is described. Application to the enantioselective synthesis of homoproline, homopipecolic acid, and pelletierine has been accomplished.

  描述了使用有机催化的分子内杂原子迈克尔加成构建对映体富集的吡咯烷、二氢吲哚和哌啶环的改进方案。已完成对高脯氨酸、高哌可酸和匹莱林的对映选择性合成的应用。
• The chiral total synthesis of (–)-oncinotine
  作者：Hiroji Ina、Masayuki Ito、Chihiro Kibayashi

  DOI：10.1039/c39950001015

  日期：——

  The first chiral synthesis of (–)-oncinotine 1 in natural form has been achieved starting from the protected (S)-N-benzyloxycarbonyl-2-piperidylacetaldehyde 3 based on a new route involving 17-membered ring formation via iminium cyclization, which establishes the 17R absolute configuration of natural 1.

  （ - ） -的第一手性合成oncinotine 1天然形式已经实现从受保护的（起始小号） - ñ -苄氧羰基-2- piperidylacetaldehyde 3基于涉及17-元环形成一个新的路由经由亚胺环化，它建立自然的17 R绝对构型1。
• Enantioselective Total Synthesis of the Macrocyclic Spermidine Alkaloid (−)-Oncinotine
  作者：Hiroji Ina、Masayuki Ito、Chihiro Kibayashi

  DOI：10.1021/jo9518258

  日期：1996.1.1

  The macrocyclic spermidine alkaloid (-)-oncinotine (1), isolated from Oncinotis nitida (Apocynaceae), was synthesized enantioselectively for the first time based on intramolecular iminium ion cyclization utilizing enantiomerically pure (2S)-N-[(benzyloxy)carbonyl]-2-piperidineacetaldehyde (8) as a chiral starting material. The required 8 was derived from the erythro adduct 16, which was obtained by diastereoselective 1,3-dipolar cycloaddition between 2,3,4,5-tetrahydropyridine 1-oxide (4) and (3S)-3-[(tert-butyldiphenylsilyl)oxy]-4-methyl-1-pentene (15). Wittig condensation of 8 with [8-(methoxycarbonyl)octyl]triphenylphosphonium iodide (21) followed by saponification provided the chiral piperidine moiety 23, which was coupled with the N-propyl-1,4-butanediamine segment 29 by using diethoxyphosphoryl cyanide in the presence of triethylamine to afford the tertiary amide 30. Conversion of 30 to the aldehyde 34 via desilylation and Swern oxidation, followed by hydrogenation over a palladium hydroxide catalyst under high dilution led to in situ formation of the transient iminium ion 35, which was further hydrogenated to form 33 in a single operation. Subsequent removal of the Boc protecting group resulted in (-)-oncinotine (1).