tert-butyl N-(4-<(3-hydroxypropyl)amino>butyl)carbamate | 164365-89-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tert-butyl N-(4-<(3-hydroxypropyl)amino>butyl)carbamate
• 英文别名: N-<4-<(tert-butoxycarbonyl)amino>butyl>-N-(3-hydroxypropyl)amine；tert-butyl N-[4-(3-hydroxypropylamino)butyl]carbamate
• CAS: 164365-89-3
• 化学式: C₁₂H₂₆N₂O₃
• 分子量: 246.35
• InChiKey: NMGVPUQYOLFAHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  70.6
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl N-(4-<(3-hydroxypropyl)amino>butyl)carbamate 在 咪唑 、 palladium dihydroxide 、 氰基磷酸二乙酯 、 四丁基氟化铵 、 氢气 、 sodium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 31.0h， 生成 {4-[(3-Hydroxy-propyl)-((R)-11-piperidin-2-yl-undecanoyl)-amino]-butyl}-carbamic acid tert-butyl ester
  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：

  N-叔丁氧羰基-1,4-丁二胺 在 sodium hydroxide 、 四甲基氯化铵 、 sodium hydride 、 potassium carbonate 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 6.75h， 生成 tert-butyl N-(4-<(3-hydroxypropyl)amino>butyl)carbamate
  参考文献：
  名称：

  电喷雾电离质谱。第三部分 的酸催化的异构化N， N'-双[（ë）-3-（4-羟基苯基）丙-2-烯酰基] spermidines由邮编反应†往最‡

  摘要：

  三个N，N'-双[（E）-3-（4-羟苯基）丙-2-烯酰基]亚精胺1-3的电喷雾串联质谱（ESI-MS / MS）显示相同的碎片离子信号。这些异构体无法通过ESI-MS / MS进行区分，因为它们的片段化模式相似。（E，E）-N-（3- [ 15N ]氨基丙基）-3，3′-双（4-羟苯基）-N，N′ -（丁烷-1，4-二基）双[prop-2-烯酰胺]（[ 15 N（1）]）-（1）的合成是为了获得有关断裂机理的进一步信息。1和[ 15 N（1）]- 1的ESI-MS / MS的比较揭示了[ 1 + H] +离子在质谱条件下的转氨基作用，即Zip反应。由于该反应，无法区分三种异构体1-3。

  DOI：

  10.1002/hlca.19960790810

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。
• Electrospray-Ionization Mass Spectrometry. Part III. Acid-Catalyzed Isomerization ofN,N?-Bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines by theZip Reaction
  作者：Laurent Bigler、Christian F. Schnider、Wenqing Hu、Manfred Hesse

  DOI：10.1002/hlca.19960790810

  日期：1996.12.11

  The electrospray tandem mass spectra (ESI-MS/MS) of the three N,N′-bis[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1–3 displayed the same fragment-ion signals. These isomers could not be differentiated by ESI-MS/MS, since their fragmentation patterns are similar. (E,E)-N-(3-[15N]Aminopropyl)-3,3′-bis(4- hydroxyphenyl)-N,N′-(butane-1,4-diyl)bis[prop-2-enamide] ([15N(1)])-(1) was synthesized in order

  三个N，N'-双[（E）-3-（4-羟苯基）丙-2-烯酰基]亚精胺1-3的电喷雾串联质谱（ESI-MS / MS）显示相同的碎片离子信号。这些异构体无法通过ESI-MS / MS进行区分，因为它们的片段化模式相似。（E，E）-N-（3- [ 15N ]氨基丙基）-3，3′-双（4-羟苯基）-N，N′ -（丁烷-1，4-二基）双[prop-2-烯酰胺]（[ 15 N（1）]）-（1）的合成是为了获得有关断裂机理的进一步信息。1和[ 15 N（1）]- 1的ESI-MS / MS的比较揭示了[ 1 + H] +离子在质谱条件下的转氨基作用，即Zip反应。由于该反应，无法区分三种异构体1-3。
• 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).