1-bromo-3-(tert-butyldimethylsilyloxy)-3-methyl-2-butanone | 244308-14-3

• 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: 1-bromo-3-(tert-butyldimethylsilyloxy)-3-methyl-2-butanone
• 英文别名: 1-Bromo-3-[tert-butyl(dimethyl)silyl]oxy-3-methylbutan-2-one
• CAS: 244308-14-3
• 化学式: C₁₁H₂₃BrO₂Si
• 分子量: 295.292
• InChiKey: HSPIEQZNUCVTCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-bromo-3-(tert-butyldimethylsilyloxy)-3-methyl-2-butanone 在 sodium hydroxide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 63.0h， 生成 (4-E)-8-(5,5-dimethyl-1-oxocyclopent-2-en-3-yl)-2-(tert-butyldimethylsilyloxy)-2-methyloct-4-en-3-one
  参考文献：
  名称：

  Nickel-Catalyzed Cyclizations of Enoate Equivalents:  Application to the Synthesis of Angular Triquinanes

  摘要：

  Unsaturated acyloxazolidinones and alpha'-silyloxy enones were found to be effective substrates in nickel-catalyzed organozinc-promoted cyclizations. Both groups served as convenient enoate equivalents, whereas methyl enoates themselves were inefficient substrates. A five-step procedure for the conversion of dimethylcyclopentenone into a highly functionalized angular triquinane was developed utilizing this observation. The key step of the procedure involves a nickel-catalyzed reductive cyclization/Dieckmann condensation sequence involving a cyclic enone tethered to an unsaturated acyloxazolidinone or alpha'-silyloxy enone. The method was applied ina formal synthesis of pentalenene, pentalenic acid, and deoxypentalenic acid.

  DOI：

  10.1021/jo9908389
• 作为产物：
  描述：

  3-羟基-3-甲基-2-丁酮 在 2,6-二甲基吡啶 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 1-bromo-3-(tert-butyldimethylsilyloxy)-3-methyl-2-butanone
  参考文献：
  名称：

  Nickel-Catalyzed Cyclizations of Enoate Equivalents:  Application to the Synthesis of Angular Triquinanes

  摘要：

  Unsaturated acyloxazolidinones and alpha'-silyloxy enones were found to be effective substrates in nickel-catalyzed organozinc-promoted cyclizations. Both groups served as convenient enoate equivalents, whereas methyl enoates themselves were inefficient substrates. A five-step procedure for the conversion of dimethylcyclopentenone into a highly functionalized angular triquinane was developed utilizing this observation. The key step of the procedure involves a nickel-catalyzed reductive cyclization/Dieckmann condensation sequence involving a cyclic enone tethered to an unsaturated acyloxazolidinone or alpha'-silyloxy enone. The method was applied ina formal synthesis of pentalenene, pentalenic acid, and deoxypentalenic acid.

  DOI：

  10.1021/jo9908389

文献信息

• Nickel-Catalyzed Cyclizations of Enoate Equivalents:  Application to the Synthesis of Angular Triquinanes
  作者：Jeongbeob Seo、Hélène Fain、Jean-Baptiste Blanc、John Montgomery

  DOI：10.1021/jo9908389

  日期：1999.8.1

  Unsaturated acyloxazolidinones and alpha'-silyloxy enones were found to be effective substrates in nickel-catalyzed organozinc-promoted cyclizations. Both groups served as convenient enoate equivalents, whereas methyl enoates themselves were inefficient substrates. A five-step procedure for the conversion of dimethylcyclopentenone into a highly functionalized angular triquinane was developed utilizing this observation. The key step of the procedure involves a nickel-catalyzed reductive cyclization/Dieckmann condensation sequence involving a cyclic enone tethered to an unsaturated acyloxazolidinone or alpha'-silyloxy enone. The method was applied ina formal synthesis of pentalenene, pentalenic acid, and deoxypentalenic acid.