<2R,2(1S),3aS>-2-<1-<(tert-butyldiphenylsilyl)oxy>-2-methylpropyl>-3,3a,4,5,6,7-hexahydro-2H-isoxazolo<2,3-a>pyridine | 143264-48-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: <2R,2(1S),3aS>-2-<1-<(tert-butyldiphenylsilyl)oxy>-2-methylpropyl>-3,3a,4,5,6,7-hexahydro-2H-isoxazolo<2,3-a>pyridine
• 英文别名: [(1S)-1-[(2R,3aS)-3,3a,4,5,6,7-hexahydro-2H-[1,2]oxazolo[2,3-a]pyridin-2-yl]-2-methylpropoxy]-tert-butyl-diphenylsilane
• CAS: 143264-48-6
• 化学式: C₂₇H₃₉NO₂Si
• 分子量: 437.698
• InChiKey: SCUKYHLCQQXUKV-DFCKQENNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.15
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <2R,2(1S),3aS>-2-<1-<(tert-butyldiphenylsilyl)oxy>-2-methylpropyl>-3,3a,4,5,6,7-hexahydro-2H-isoxazolo<2,3-a>pyridine 在 四丁基氟化铵 、 氢气 、 sodium carbonate 、 过碘酸 、 palladium dichloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 45.0 ℃ 、658.61 kPa 条件下， 反应 54.5h， 生成 (S)-2-(2-氧代乙基)-1-哌啶羧酸苯基甲酯
  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：

  ethyl (2S)-2-hydroxy-3-methylbutanoate 在 咪唑 、 四氯化钛 、 二异丁基氢化铝 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 29.0h， 生成 <2R,2(1S),3aS>-2-<1-<(tert-butyldiphenylsilyl)oxy>-2-methylpropyl>-3,3a,4,5,6,7-hexahydro-2H-isoxazolo<2,3-a>pyridine
  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

• 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。
• 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).