6,6-diethoxy-2-methoxy-9-methoxymethyl-9,12a-dimethyl-5,6,7a,8,8a,9,10,11,12,12a-decahydro-4H-7-oxa-6-silacyclohepta[jk]phenanthrene | 287919-17-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 6,6-diethoxy-2-methoxy-9-methoxymethyl-9,12a-dimethyl-5,6,7a,8,8a,9,10,11,12,12a-decahydro-4H-7-oxa-6-silacyclohepta[jk]phenanthrene
• CAS: 287919-17-9
• 化学式: C₂₅H₄₀O₅Si
• 分子量: 448.675
• InChiKey: JCPLOVNQDUXPOL-ZCAIMPEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  31.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  6,6-diethoxy-2-methoxy-9-methoxymethyl-9,12a-dimethyl-5,6,7a,8,8a,9,10,11,12,12a-decahydro-4H-7-oxa-6-silacyclohepta[jk]phenanthrene 在 dimethyl sulfide borane 、 potassium fluoride 、 双氧水 、 碳酸氢钠 作用下， 以 二氯甲烷 、 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成 (7aR,8S,11aS)-4-(2-Hydroxy-ethyl)-2-methoxy-8-methoxymethyl-8,11a-dimethyl-7a,8,9,10,11,11a-hexahydro-7H-5-oxa-dibenzo[a,c]cyclohepten-6-one
  参考文献：
  名称：

  Functionalisation of Alkylalkoxysilanes. Studies Towards Annulations of Diterpenoids

  摘要：

  Ortho-(2-triethoxysilylethyl) derivatives of aryl ketones undergo oxidative desilylation with H2O2. Tetralone derivatives have served as model substrates for 14-2-(triethoxysilylethyl)-7-oxopodocarpanes, which have been converted into 2-arylethanols in a four-step sequence (BH3. BMS, H2O2, Et3SiH/CF3COOH, TBAF) without isolation of intermediate products (oxasilepin, diol, trifluoroacetate). Use of the 14-(2-diethoxysilylmethyl) analogue improved the overall yield significantly (75 versus 40%). Re-oxidation of ring B with CAN gave the Delta(5)-7-oxo derivative, which was converted into an enone-aldehyde by treatment with Collins' reagent. The conjugated alkene was reduced stereoselectively with SmI2, which, however, did not promote pinacol coupling of the resulting 1,5-keto aldehyde. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00302-1
• 作为产物：
  描述：

  14-(2-trietoxysilylethyl)-12,19-dimethoxypodocarpa-8,11,13-trien-7-one 在 红铝 作用下， 以 甲苯 为溶剂， 以322 mg的产率得到6,6-diethoxy-2-methoxy-9-methoxymethyl-9,12a-dimethyl-5,6,7a,8,8a,9,10,11,12,12a-decahydro-4H-7-oxa-6-silacyclohepta[jk]phenanthrene
  参考文献：
  名称：

  Functionalisation of Alkylalkoxysilanes. Studies Towards Annulations of Diterpenoids

  摘要：

  Ortho-(2-triethoxysilylethyl) derivatives of aryl ketones undergo oxidative desilylation with H2O2. Tetralone derivatives have served as model substrates for 14-2-(triethoxysilylethyl)-7-oxopodocarpanes, which have been converted into 2-arylethanols in a four-step sequence (BH3. BMS, H2O2, Et3SiH/CF3COOH, TBAF) without isolation of intermediate products (oxasilepin, diol, trifluoroacetate). Use of the 14-(2-diethoxysilylmethyl) analogue improved the overall yield significantly (75 versus 40%). Re-oxidation of ring B with CAN gave the Delta(5)-7-oxo derivative, which was converted into an enone-aldehyde by treatment with Collins' reagent. The conjugated alkene was reduced stereoselectively with SmI2, which, however, did not promote pinacol coupling of the resulting 1,5-keto aldehyde. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00302-1