(1R,2S,4S,5'R,6R,7S,8R,9S,10E,12S,13S,16S,18S)-10-[[tert-butyl(dimethyl)silyl]hydrazinylidene]-16-[tert-butyl(dimethyl)silyl]oxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane] | 690275-05-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,2S,4S,5'R,6R,7S,8R,9S,10E,12S,13S,16S,18S)-10-[[tert-butyl(dimethyl)silyl]hydrazinylidene]-16-[tert-butyl(dimethyl)silyl]oxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane]
• CAS: 690275-05-9
• 化学式: C₃₉H₇₂N₂O₃Si₂
• 分子量: 673.183
• InChiKey: SVYQMXZUZSTLBP-HWXXKVGRSA-N

物化性质

• 沸点：
  641.4±65.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.38
• 重原子数：
  46
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  52.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2S,4S,5'R,6R,7S,8R,9S,10E,12S,13S,16S,18S)-10-[[tert-butyl(dimethyl)silyl]hydrazinylidene]-16-[tert-butyl(dimethyl)silyl]oxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane] 在 potassium tert-butylate 、 叔丁醇 作用下， 以 二甲基亚砜 为溶剂， 反应 24.0h， 以95%的产率得到剑麻皂素
  参考文献：
  名称：

  Practical Procedures for the Preparation of N-tert-Butyldimethylsilylhydrazones and Their Use in Modified Wolff−Kishner Reductions and in the Synthesis of Vinyl Halides and gem-Dihalides

  摘要：

  In this work we develop practical chemistry for the preparation of N-tert-butyldimethylsilylhydrazone (TBSH) derivatives from carbonyl-containing compounds and show that these products serve as superior alternatives to simple hydrazones in Wolff-Kishner-type reduction reactions, in the Barton vinyl iodide preparation, in the synthesis of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides. In our new procedure for silyl hydrazone synthesis, aliphatic and aromatic ketones and aldehydes are shown to undergo highly efficient coupling (typically >95% yield) to form the corresponding TBSH derivatives when combined with equimolar amounts of 1,2-bis(tert-butyldimethylsilyl)hydrazine (BTBSH) and a catalytic quantity of scandium trifluoromethanesulfonate (typically, 0.01 mol %), neat, or in solvent. Optimized procedures are provided for the use of TBSH derivatives in a Wolff-Kishner-type reduction protocol that proceeds at low temperature (23-100 degreesC) and in a single reaction flask. Similarly, protocols for the use of TBSH derivatives as precursors to vinyl halides and gem-dihalides are described in detail.

  DOI：

  10.1021/ja049694s
• 作为产物：
  描述：

  1,2-双(叔丁基二甲基硅烷基)肼 、 海柯吉宁 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 氯仿 为溶剂， 反应 20.0h， 以93%的产率得到(1R,2S,4S,5'R,6R,7S,8R,9S,10E,12S,13S,16S,18S)-10-[[tert-butyl(dimethyl)silyl]hydrazinylidene]-16-[tert-butyl(dimethyl)silyl]oxy-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icosane-6,2'-oxane]
  参考文献：
  名称：

  Practical Procedures for the Preparation of N-tert-Butyldimethylsilylhydrazones and Their Use in Modified Wolff−Kishner Reductions and in the Synthesis of Vinyl Halides and gem-Dihalides

  摘要：

  In this work we develop practical chemistry for the preparation of N-tert-butyldimethylsilylhydrazone (TBSH) derivatives from carbonyl-containing compounds and show that these products serve as superior alternatives to simple hydrazones in Wolff-Kishner-type reduction reactions, in the Barton vinyl iodide preparation, in the synthesis of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides. In our new procedure for silyl hydrazone synthesis, aliphatic and aromatic ketones and aldehydes are shown to undergo highly efficient coupling (typically >95% yield) to form the corresponding TBSH derivatives when combined with equimolar amounts of 1,2-bis(tert-butyldimethylsilyl)hydrazine (BTBSH) and a catalytic quantity of scandium trifluoromethanesulfonate (typically, 0.01 mol %), neat, or in solvent. Optimized procedures are provided for the use of TBSH derivatives in a Wolff-Kishner-type reduction protocol that proceeds at low temperature (23-100 degreesC) and in a single reaction flask. Similarly, protocols for the use of TBSH derivatives as precursors to vinyl halides and gem-dihalides are described in detail.

  DOI：

  10.1021/ja049694s