<11(2S)>-N-<4-<(tert-butoxycarbonyl)amino>butyl>-N-<3-<(tert-butyldimethylsilyl)oxy>propyl>-11-<2-piperidyl>-9-undecenamide | 164365-93-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: <11(2S)>-N-<4-<(tert-butoxycarbonyl)amino>butyl>-N-<3-<(tert-butyldimethylsilyl)oxy>propyl>-11-<2-piperidyl>-9-undecenamide
• 英文别名: benzyl (2S)-2-[(Z)-11-[3-[tert-butyl(dimethyl)silyl]oxypropyl-[4-[(2-methylpropan-2-yl)oxycarbonylamino]butyl]amino]-11-oxoundec-2-enyl]piperidine-1-carboxylate
• CAS: 164365-93-9
• 化学式: C₄₂H₇₃N₃O₆Si
• 分子量: 744.144
• InChiKey: ZLYAXAWERGLLPH-AFRGNODISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  52
• 可旋转键数：
  26
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  97.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  <11(2S)>-N-<4-<(tert-butoxycarbonyl)amino>butyl>-N-<3-<(tert-butyldimethylsilyl)oxy>propyl>-11-<2-piperidyl>-9-undecenamide 在 盐酸 、 palladium dihydroxide 、 草酰氯 、 四丁基氟化铵 、 氢气 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 103.0h， 生成 (15aR)-4-(4-氨基丁基)二十氢吡啶并[1,2-e][1,5]二氮杂环十七烷-5-酮
  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：

  (S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯 在 氢氧化钾 、 氰基磷酸二乙酯 、 potassium tert-butylate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.33h， 生成 <11(2S)>-N-<4-<(tert-butoxycarbonyl)amino>butyl>-N-<3-<(tert-butyldimethylsilyl)oxy>propyl>-11-<2-piperidyl>-9-undecenamide
  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

文献信息

• 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).