2α,4α-dimethyl-3α-((triethylsilyl)oxy)-6β,7β-dioxabicyclo<3.2.2>non-8-ene | 146951-57-7

• 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: 2α,4α-dimethyl-3α-((triethylsilyl)oxy)-6β,7β-dioxabicyclo<3.2.2>non-8-ene
• CAS: 146951-57-7
• 化学式: C₁₅H₂₈O₃Si
• 分子量: 284.471
• InChiKey: ZPPOBGUQOFBUCZ-AZOBVAEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  2α,4α-dimethyl-3α-((triethylsilyl)oxy)-6β,7β-dioxabicyclo<3.2.2>non-8-ene 在 硫脲 作用下， 以 甲醇 为溶剂， 反应 13.0h， 以63%的产率得到5α,7α-dimethyl-6α-((triethylsilyl)oxy)cyclohept-2-ene-1β,4β-diol
  参考文献：
  名称：

  Organoiron-templated stereocontrolled alkylation of enolates: functionalization of cycloheptadienones to give useful synthetic building blocks

  摘要：

  Conversion of eta4-cycloheptatriene-Fe(CO)2P(OPh)3 to ketocycloheptadiene-Fe(CO)2P(OPh)3 complex 7 was accomplished by hydroboration followed by Swern oxidation. Methylation and hydroxylation of the enolate from 7 proceeds with complete stereoselectivity, anti to the metal moiety, and introduction of two methyl or hydroxyl groups at the alpha and alpha' positions was accomplished in high overall yield. Reduction of the ketone group on these complexes occurs with high stereoselectivity and is controlled by the boat conformation adopted by these complexes. The product of these reaction sequences were demetalated to give cycloheptadiene derivatives that were further functionalized to give a C(9)-C(14) subunit of calyculin A1 and a C(19)-C(25) subunit of swinholide A.

  DOI：

  10.1021/jo00057a041
• 作为产物：
  描述：

  6α-hydroxy-5α,7α-dimethylcyclohepta-1,3-diene 在 氧气 、 tetraphenylporphyrin 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 2α,4α-dimethyl-3α-((triethylsilyl)oxy)-6β,7β-dioxabicyclo<3.2.2>non-8-ene
  参考文献：
  名称：

  Organoiron-templated stereocontrolled alkylation of enolates: functionalization of cycloheptadienones to give useful synthetic building blocks

  摘要：

  Conversion of eta4-cycloheptatriene-Fe(CO)2P(OPh)3 to ketocycloheptadiene-Fe(CO)2P(OPh)3 complex 7 was accomplished by hydroboration followed by Swern oxidation. Methylation and hydroxylation of the enolate from 7 proceeds with complete stereoselectivity, anti to the metal moiety, and introduction of two methyl or hydroxyl groups at the alpha and alpha' positions was accomplished in high overall yield. Reduction of the ketone group on these complexes occurs with high stereoselectivity and is controlled by the boat conformation adopted by these complexes. The product of these reaction sequences were demetalated to give cycloheptadiene derivatives that were further functionalized to give a C(9)-C(14) subunit of calyculin A1 and a C(19)-C(25) subunit of swinholide A.

  DOI：

  10.1021/jo00057a041

文献信息

• Stereocontrolled multiple functionalization of cycloheptadienoneiron complexes via enolate alkylation
  作者：Anthony J. Pearson、Kieyoung Chang

  DOI：10.1039/c39910000394

  日期：——

  Alkylation of enolates from tricarbonyl(6-oxocycloheptadiene)iron occurs with complete stereoselectivity trans to the metal, while reduction of the ketone occurs with stereochemistry dictated by the boat conformation adopted by these molecules.

  三羰基(6-氧代环庚二烯)铁对烯醇的烷基化反应具有完全的立体选择性，而酮的还原反应则由这些分子所采用的舟形构象决定其立体化学性质。