6β-<(tert-butyldimethylsilyl)oxy>-5α,7α-dimethoxycyclohepta-1,3-diene | 142458-28-4

• 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: 6β-<(tert-butyldimethylsilyl)oxy>-5α,7α-dimethoxycyclohepta-1,3-diene
• CAS: 142458-28-4
• 化学式: C₁₅H₂₈O₃Si
• 分子量: 284.471
• InChiKey: NNHGHVQSZDCQLF-WDNDVIMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6β-<(tert-butyldimethylsilyl)oxy>-5α,7α-dimethoxycyclohepta-1,3-diene 在 吡啶 、 4-二甲氨基吡啶 、 氧气 、 tetraphenylporphyrin 、 硫脲 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 167.0h， 生成 (3S,4R,5S,6S,7R)-3-acetoxy-5-<(tert-butyldimethylsilyl)oxy>-4,5-dimethoxy-7-<(R)-α-methoxy-α-(trifluoromethyl)phenylacetoxy>cyclohept-1-ene
  参考文献：
  名称：

  Approaches to the synthesis of heptitol derivatives via iron-mediated stereocontrolled functionalization of cycloheptatrienone

  摘要：

  Stereocontrolled reduction of tropone-Fe(CO)3 (9) followed by alcohol protection gives the [(trialkylsilyl)oxy]cycloheptatriene complex 11. Osmylation of 11 proceeds with complete stereoselectivity to give the protected trihydroxycycloheptadiene complex 12, treatment of which with acid in the presence of methanol (generated in situ) gives the symmetrically trioxygenated diene complex 15. Decomplexation of these complexes, followed by stereocontrolled diene oxygenation and ring cleavage, provides methodology for the construction of heptitol derivatives. Conversion of complex 15 to ether-substituted dienyl-Fe(CO)3 cationic complexes was studied. These complexes react with nucleophiles to give diene-, dienyl-, or enediyl-Fe(CO)2L complexes, depending on the nature of the nucleophile and the spectator ligand.

  DOI：

  10.1021/jo00040a043
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 十二/十四烷基二甲基氧化胺 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以91%的产率得到6β-<(tert-butyldimethylsilyl)oxy>-5α,7α-dimethoxycyclohepta-1,3-diene
  参考文献：
  名称：

  Approaches to the synthesis of heptitol derivatives via iron-mediated stereocontrolled functionalization of cycloheptatrienone

  摘要：

  Stereocontrolled reduction of tropone-Fe(CO)3 (9) followed by alcohol protection gives the [(trialkylsilyl)oxy]cycloheptatriene complex 11. Osmylation of 11 proceeds with complete stereoselectivity to give the protected trihydroxycycloheptadiene complex 12, treatment of which with acid in the presence of methanol (generated in situ) gives the symmetrically trioxygenated diene complex 15. Decomplexation of these complexes, followed by stereocontrolled diene oxygenation and ring cleavage, provides methodology for the construction of heptitol derivatives. Conversion of complex 15 to ether-substituted dienyl-Fe(CO)3 cationic complexes was studied. These complexes react with nucleophiles to give diene-, dienyl-, or enediyl-Fe(CO)2L complexes, depending on the nature of the nucleophile and the spectator ligand.

  DOI：

  10.1021/jo00040a043

文献信息

• Stereocontrolled functionalization of cycloheptatrieneiron complexes. Synthesis of polyhydroxylated cycloheptane derivatives
  作者：Anthony J. Pearson、Kumar Srinivasan

  DOI：10.1039/c39910000392

  日期：——

  Osmylation and hydroboration of η4-cycloheptatriene–Fe(CO)2L complexes [L = CO or P(OPh)3] proceeds with excellent regio- and stereo-selectivity, owing to the profound directing effects of the Fe(CO)2L group.

  η4-环庚三烯-Fe(CO)2L 复合物[L = CO 或 P(OPh)3]的锇化和烃硼化过程具有极佳的区域和立体选择性，这是由于 Fe(CO)2L 基团具有深远的导向作用。
• General access to polyhydroxylated nortropane derivatives through hetero diels -alder cycloaddition
  作者：Josette Soulié、Jean-François Betzer、Benoit Muller、Jean-Yves Lallemand

  DOI：10.1016/0040-4039(95)02074-8

  日期：1995.12

  Title compounds were prepared by the intramolecular cyclisation of 4-aminocycloheptanones as the key step. The functionalisation of the iron-complexed tropone gave cyclohepta-1,3-dienes. The 4-aminocycloheptanones result from a heterocycloaddition between an acylnitroso compound and a eyclohepta-1,3-diene.

  通过将4-氨基环庚酮的分子内环化作为关键步骤来制备标题化合物。铁络合物的托酮的官能化得到环庚-1，3-二烯。4-氨基环庚酮是由酰基亚硝基化合物与叶庚基-1,3-二烯之间的杂环加成产生的。