dimethyl (S)-(-)-6-(tert-butyldiphenylsilyloxymethyl)-5,6-dihydro-4H-pyridine-1,2-dicarboxylate | 442202-05-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl (S)-(-)-6-(tert-butyldiphenylsilyloxymethyl)-5,6-dihydro-4H-pyridine-1,2-dicarboxylate
• 英文别名: dimethyl (2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,4-dihydro-2H-pyridine-1,6-dicarboxylate
• CAS: 442202-05-3
• 化学式: C₂₆H₃₃NO₅Si
• 分子量: 467.637
• InChiKey: HMVPVFOGZWIWOD-FQEVSTJZSA-N

物化性质

• 沸点：
  528.2±50.0 °C(predicted)
• 密度：
  1.14±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl (S)-(-)-6-(tert-butyldiphenylsilyloxymethyl)-5,6-dihydro-4H-pyridine-1,2-dicarboxylate 在 lithium hydroxide 、 甲基锂 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 为溶剂， 反应 4.83h， 生成 2-O-ethoxycarbonyl 1-O-methyl (2R,3S,6S)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-ethenylpiperidine-1,2-dicarboxylate
  参考文献：
  名称：

  Stereodivergent Process for the Synthesis of the Decahydroquinoline Type of Dendrobatid Alkaloids

  摘要：

  A flexible and stereodivergent synthesis of the cis- and trans-fused 2,5-disubstituted octahydroquinolinone ring systems bearing all four stereogenic centers for the synthesis of the decahydroquinoline type of dendrobatid alkaloids has been achieved. The strategy involves stereoselective and stereodivergent construction of 2,3,6-trisubstituted piperidine ring systems using the Michael type of conjugate addition reaction to the enaminoesters 1 and 3, the intramolecular aldol type of cyclization reaction of keto aldehydes 11 and 12, and ring-closing metathesis of 21 as key steps.

  DOI：

  10.1021/jo025929b
• 作为产物：
  描述：

  (S)-6-((tert-butyldiphenylsilyloxy)methyl)piperidin-2-one 在 四(三苯基膦)钯 、 正丁基锂 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 dimethyl (S)-(-)-6-(tert-butyldiphenylsilyloxymethyl)-5,6-dihydro-4H-pyridine-1,2-dicarboxylate
  参考文献：
  名称：

  2,3,5,6-四取代哌啶环系统的立体发散合成：从毒蛙合成生物碱223A和205B的应用

  摘要：

  2,3,5,6-四取代的哌啶环系统的立体发散性合成已通过适当的烯氨基酯的顺序立体控制的迈克尔型共轭加成反应来实现。该方法已应用于毒蛙生物碱223A和205B的总合成。修订了天然223A在6位的相对立体化学，并通过本合成方法确定了天然205B的绝对立体化学。

  DOI：

  10.1016/j.tet.2004.05.039

文献信息

• Total Synthesis of the Antipode of Alkaloid 205 B
  作者：Naoki Toyooka、Ayako Fukutome、Hiroyuki Shinoda、Hideo Nemoto

  DOI：10.1002/anie.200351906

  日期：2003.8.18
• Synthesis of Alkaloid 223A and a Structural Revision
  作者：Naoki Toyooka、Ayako Fukutome、Hideo Nemoto、John W. Daly、Thomas F. Spande、H. Martin Garraffo、Tetsuo Kaneko

  DOI：10.1021/ol025775m

  日期：2002.5.1

  [GRAPHICS]Synthesis of alkaloid 223A has been achieved by sequential use of our original conjugate addition reaction to enaminoesters as the key step. The proposed structure for natural 223A (A, absolute configuration unknown) was revised to B, and the relative stereostructure was determined to be 5R*,6R*,8R*,9S* by the present synthesis.
• Stereodivergent synthesis of the 2,3,5,6-tetrasubstituted piperidine ring system: an application to the synthesis of alkaloids and from poison frogs
  作者：Naoki Toyooka、Ayako Fukutome、Hiroyuki Shinoda、Hideo Nemoto

  DOI：10.1016/j.tet.2004.05.039

  日期：2004.7

  Stereodivergent synthesis of the 2,3,5,6-tetrasubstituted piperidine ring system has been achieved by sequential stereocontrolled Michael-type conjugate addition reaction of appropriate enaminoesters. This methodology has been applied to the total syntheses of the poison frog alkaloids 223A and 205B. The relative stereochemistry of natural 223A at the 6-position was revised, and the absolute stereochemistry

  2,3,5,6-四取代的哌啶环系统的立体发散性合成已通过适当的烯氨基酯的顺序立体控制的迈克尔型共轭加成反应来实现。该方法已应用于毒蛙生物碱223A和205B的总合成。修订了天然223A在6位的相对立体化学，并通过本合成方法确定了天然205B的绝对立体化学。
• Stereodivergent Process for the Synthesis of the Decahydroquinoline Type of Dendrobatid Alkaloids
  作者：Naoki Toyooka、Maiko Okumura、Hideo Nemoto

  DOI：10.1021/jo025929b

  日期：2002.8.1

  A flexible and stereodivergent synthesis of the cis- and trans-fused 2,5-disubstituted octahydroquinolinone ring systems bearing all four stereogenic centers for the synthesis of the decahydroquinoline type of dendrobatid alkaloids has been achieved. The strategy involves stereoselective and stereodivergent construction of 2,3,6-trisubstituted piperidine ring systems using the Michael type of conjugate addition reaction to the enaminoesters 1 and 3, the intramolecular aldol type of cyclization reaction of keto aldehydes 11 and 12, and ring-closing metathesis of 21 as key steps.