[3aR(3aα,4α,5β,6aα)]-(-)-5-(benzoyloxy)hexahydro-2-oxo-2H-cyclopenta[b]furan-4-carboxaldehyde N-tert-butyldimethylsilylhydrazone

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [3aR(3aα,4α,5β,6aα)]-(-)-5-(benzoyloxy)hexahydro-2-oxo-2H-cyclopenta[b]furan-4-carboxaldehyde N-tert-butyldimethylsilylhydrazone
• 英文别名: [(3aR,4S,5R,6aS)-4-[(Z)-[[tert-butyl(dimethyl)silyl]hydrazinylidene]methyl]-2-oxo-3,3a,4,5,6,6a-hexahydrocyclopenta[b]furan-5-yl] benzoate
• 化学式: C₂₁H₃₀N₂O₄Si
• 分子量: 402.566
• InChiKey: ASPSIULHCXMOCC-HEMRBOINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  77
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 alkaline earth salt of/the/ methylsulfuric acid 在 scandium tris(trifluoromethanesulfonate) 、 肼 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 [3aR(3aα,4α,5β,6aα)]-(-)-5-(benzoyloxy)hexahydro-2-oxo-2H-cyclopenta[b]furan-4-carboxaldehyde N-tert-butyldimethylsilylhydrazone
  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

文献信息

• Practical Procedures for the Preparation of <i>N</i>-<i>tert</i>-Butyldimethylsilylhydrazones and Their Use in Modified Wolff−Kishner Reductions and in the Synthesis of Vinyl Halides and <i>g</i><i>em</i>-Dihalides
  作者：Michael E. Furrow、Andrew G. Myers

  DOI：10.1021/ja049694s

  日期：2004.5.1

  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.