(R)-methyl 2-((R)-3-bromo-4-oxocyclopent-2-enyl)-2-(tertbutyldimethylsilyloxy)ethanoate | 1335099-04-1

• 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: (R)-methyl 2-((R)-3-bromo-4-oxocyclopent-2-enyl)-2-(tertbutyldimethylsilyloxy)ethanoate
• 英文别名: methyl (2R)-2-[(1R)-3-bromo-4-oxocyclopent-2-en-1-yl]-2-[tert-butyl(dimethyl)silyl]oxyacetate
• CAS: 1335099-04-1
• 化学式: C₁₄H₂₃BrO₄Si
• 分子量: 363.324
• InChiKey: AYDZSCMSBOWXOP-JOYOIKCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-methyl 2-((R)-3-bromo-4-oxocyclopent-2-enyl)-2-(tertbutyldimethylsilyloxy)ethanoate 在 六甲基磷酰三胺 、 sodium tetrahydroborate 、 偶氮二异丁腈 、 四甲基乙二胺 、 cerium(III) chloride heptahydrate 、 甲基锂 、 三正丁基氢锡 、 lead(IV) tetraacetate 、 sodium hexamethyldisilazane 、 copper(l) cyanide 、 草酸 、 四氯化钛 、 N-甲基吗啉氧化物 、 lead(II) chloride 、 锌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 、 苯 为溶剂， 反应 19.67h， 生成 methyl (3R,4R)-3-[(1R)-1-[(1R,3aR,8aS)-1,4,4-trimethyl-8-methylidene-3,3a,5,6,7,8a-hexahydro-2H-azulen-1-yl]-2-oxoethyl]-4-[tert-butyl(dimethyl)silyl]oxy-5-oxohexanoate
  参考文献：
  名称：

  Enantioselective Total Synthesis of Aplyviolene

  摘要：

  The enantioselective total synthesis of the rearranged spongian diterpene aplyviolene has been completed in 14 steps from the known hydroazulenone 8. The key junction of the hydrocarbon and oxygenated fragments to form the critical C8 quaternary carbon stereocenter and set the stage for elaborating the delicate bicyclic lactone functionality was accomplished in high yield and exquisite stereoselectivity by Michael addition of an enantioenriched hydroazulenone enolate to an enantiopure alpha-bromocyclopentenone.

  DOI：

  10.1021/ja208018s
• 作为产物：
  描述：

  (R)-methyl 2-(tert-butyldimethylsilyloxy)-2-((R)-4-oxocyclopent-2-enyl)ethanoate 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以84%的产率得到(R)-methyl 2-((R)-3-bromo-4-oxocyclopent-2-enyl)-2-(tertbutyldimethylsilyloxy)ethanoate
  参考文献：
  名称：

  Enantioselective Total Synthesis of Aplyviolene

  摘要：

  The enantioselective total synthesis of the rearranged spongian diterpene aplyviolene has been completed in 14 steps from the known hydroazulenone 8. The key junction of the hydrocarbon and oxygenated fragments to form the critical C8 quaternary carbon stereocenter and set the stage for elaborating the delicate bicyclic lactone functionality was accomplished in high yield and exquisite stereoselectivity by Michael addition of an enantioenriched hydroazulenone enolate to an enantiopure alpha-bromocyclopentenone.

  DOI：

  10.1021/ja208018s

文献信息

• Enantioselective Total Synthesis of Aplyviolene
  作者：Martin J. Schnermann、Larry E. Overman

  DOI：10.1021/ja208018s

  日期：2011.10.19

  The enantioselective total synthesis of the rearranged spongian diterpene aplyviolene has been completed in 14 steps from the known hydroazulenone 8. The key junction of the hydrocarbon and oxygenated fragments to form the critical C8 quaternary carbon stereocenter and set the stage for elaborating the delicate bicyclic lactone functionality was accomplished in high yield and exquisite stereoselectivity by Michael addition of an enantioenriched hydroazulenone enolate to an enantiopure alpha-bromocyclopentenone.