(3S)-3-<(tert-butyldiphenylsilyl)oxy>-4-methyl-1-pentene | 143264-41-9

• 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: (3S)-3-<(tert-butyldiphenylsilyl)oxy>-4-methyl-1-pentene
• 英文别名: (3S)-3-(tert-butyldiphenylsilyloxy)-4-methyl-1-pentene；tert-butyl-[(3S)-4-methylpent-1-en-3-yl]oxy-diphenylsilane
• CAS: 143264-41-9
• 化学式: C₂₂H₃₀OSi
• 分子量: 338.565
• InChiKey: WHCMWMIHLHQJDR-OAQYLSRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S)-3-<(tert-butyldiphenylsilyl)oxy>-4-methyl-1-pentene 在 palladium dichloride 四丁基氟化铵 、 氢气 、 sodium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 <2S,2(2R),2(3S)>-N-<(benzyloxy)carbonyl>-2-(2,3-dihydroxy-4-methylpentyl)piperidine
  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
• 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 为溶剂， 反应 15.0h， 生成 (3S)-3-<(tert-butyldiphenylsilyl)oxy>-4-methyl-1-pentene
  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。
• Rhodium-Catalyzed Methylenation of Aldehydes
  作者：Hélène Lebel、Valérie Paquet

  DOI：10.1021/ja038112o

  日期：2004.1.1

  The rhodium-catalyzed methylenation of aldehydes using trimethylsilyldiazomethane and triphenylphosphine produces a variety of terminal alkenes in excellent yields. These mild and nonbasic reaction conditions allow the conversion of enolizable substrates (keto aldehydes and nonracemic alpha-substituted aldehydes) to terminal alkenes without epimerization. Optimization of the reaction conditions led

  使用三甲基甲硅烷基重氮甲烷和三苯基膦对醛进行铑催化的亚甲基化反应，以优异的收率生成多种末端烯烃。这些温和且非碱性的反应条件允许可烯醇化的底物（酮醛和非外消旋 α 取代醛）转化为末端烯烃，而无需差向异构化。反应条件的优化得出的结论是，多种铑 (I) 源可用作催化剂。还研究了溶剂对反应的影响，表明虽然四氢呋喃是最好的溶剂，但也可以使用其他溶剂。系统的反应性很大程度上取决于膦试剂的性质。还描述了易于去除的膦的使用。
• Rhodium-Catalyzed Synthesis of Terminal Alkenes
  作者：Hélène Lebel、Valérie Paquet

  DOI：10.1055/s-2004-834920

  日期：——

  Terminal alkenes have been efficiently prepared via a rhodium-catalyzed olefination procedure using Wilkinson’s catalyst in the presence of triphenylphosphine, 2-propanol and trimethylsilyldiazomethane. Optimized reaction conditions are described for aldehydes and ketones, as well as alternative work up procedures.

  端烯烃已通过使用Wilkinson催化剂的铑催化的烯化反应高效制备，该反应在三苯基膦、2-丙醇和三甲基硅基重氮甲烷的存在下进行。本文描述了醛和酮的优化反应条件，以及可选的后处理程序。
• 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).