(2S,3R)-3-(tert-butyldimethylsiloxy)-2-methyl-2,3,4,6,7,8-hexahydroquinolin-5(1H)-one | 782498-14-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (2S,3R)-3-(tert-butyldimethylsiloxy)-2-methyl-2,3,4,6,7,8-hexahydroquinolin-5(1H)-one
• 英文别名: (2S,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2-methyl-2,3,4,6,7,8-hexahydro-1H-quinolin-5-one
• CAS: 782498-14-0
• 化学式: C₁₆H₂₉NO₂Si
• 分子量: 295.497
• InChiKey: BVBTVDRWVQPZLT-XHDPSFHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R)-3-(tert-butyldimethylsiloxy)-2-methyl-2,3,4,6,7,8-hexahydroquinolin-5(1H)-one 在 platinum on activated charcoal 水 、 氢气 、 sodium hexamethyldisilazane 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 、 戴斯-马丁氧化剂 、 溶剂黄146 、 三氟乙酸 、 三氯乙酸 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 乙腈 为溶剂， -78.0~50.0 ℃ 、8.11 MPa 条件下， 反应 100.33h， 生成 (2S,3R,4aS,5S,8aR)-2-methyl-3-(tert-butyldimethylsilyloxy)-5-[(1E,3E)-octadien-1-yl]decahydroquinoline
  参考文献：
  名称：

  Lepadins B，d，e和h的全合成；确定后三种生物碱的构型。

  摘要：

  DOI：

  10.1002/anie.200460128
• 作为产物：
  描述：

  (1S,2S)-3-Bromo-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-propylamine 在 三乙胺 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 14.0h， 生成 (2S,3R)-3-(tert-butyldimethylsiloxy)-2-methyl-2,3,4,6,7,8-hexahydroquinolin-5(1H)-one
  参考文献：
  名称：

  Facile Entry to Substituted Decahydroquinoline Alkaloids. Total Synthesis of Lepadins A−E and H

  摘要：

  Condensation of a L-alanine derived delta-bromo-beta-silyloxy-propylamine with 1,3-cyclohexadione followed by alkylative cyclization produces a bicyclic enone. Diastereoselective Pt/C-catalyzed hydrogenation of this enone in HOAc provides a 5-oxo-cis-fused decahydroquinoline. Wittig olefination of this decahydroquinoline and subsequent epimerization of the resulting 5-formyl intermediate gives rise to a 5-beta-formyl decahydroquinoline exclusively. In a parallel procedure, Peterson reaction of this decahydroquinoline and subsequent hydrogenation of the generated 5-exo-olefin provides a decahydroquinoline with a 5-alpha-substituent predominantly. For these two diastereoselective processes, using the intermediates without N-protection as the substrates is essential because the corresponding N-Boc intermediates give poor diastereoselectivity. The intermediate with beta-form side chain is further converted into lepadins A-C via carbon chain elongation, while the intermediate with alpha-form side chain is transformed into lepadins D, E, and H and corresponding 5'-epimers via connection with two sulfones generated from two Sharpless epoxidation products. By comparison of the rotations and NMR data, the stereochemistry of lepadins D, E, and H is assigned as 2S, 3R, 4aS, 5S, 8aR, 5'R.

  DOI：

  10.1021/jo061070c

文献信息

• Stereodivergent Approach to Both C2,8a-syn and C2,8a-anti Relative Stereochemical Manifolds in the Lepadin Family via a TiCl4-Promoted Aza-[3+3] Annulation
  作者：Richard Hsung、Gang Li、Lauren Carlson、Irina Sagamanova、Brian Slafer、Claudio Gilardi、Heather Sklenicka、Nadiya Sydorenko

  DOI：10.1055/s-0029-1216920

  日期：2009.9

  Details in developing a stereodivergent approach to the lepadin family and establishing an entry to both C2,8a-syn and C2,8a-anti relative stereochemical manifolds through a common intermediate are described here. This works paves the foundation for constructing all members of the lepadin family, which consists of three subsets based on an array of interesting relative configurations. These efforts underline the prominence of aza-[3+3] annulation as a unified strategy in alkaloid synthesis.

  本文详细描述了开发立体选择性方法合成lepadin家族化合物，并通过一个共同中间体建立了C2,8a-syn和C2,8a-anti相对立体化学空间的入口。这项工作为构建基于一系列有趣相对构型的三个亚组的lepadin家族所有成员奠定了基础。这些努力突显了氮杂-[3+3]环化作为生物碱合成统一策略的重要性。
• Total Synthesis of (+)-Lepadin F
  作者：Gang Li、Richard P. Hsung、Brian W. Slafer、Irina K. Sagamanova

  DOI：10.1021/ol802068q

  日期：2008.11.6

  An enantioselective total synthesis of (+)-lepadin F is described. The synthetic sequence features an intermolecular aza-[3 + 3] annulation, homologation of a vinylogous amide via Eschenmoser's episulfide contraction, and a highly stereoselective hydrogenation essential for achieving the 1,3-anti relative stereochemistry at C2 and C8a.