1,8-dimethoxy-4-(ethyl-3'-formylpropanoate)-3-<2-(trimethylsilyl)ethoxymethoxy>-9H-xanthene-Δ^9,δ-butane | 231621-44-6

• 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: 1,8-dimethoxy-4-(ethyl-3'-formylpropanoate)-3-<2-(trimethylsilyl)ethoxymethoxy>-9H-xanthene-Δ^9,δ-butane
• 英文别名: ethyl 3-[9-butylidene-1,8-dimethoxy-3-(2-trimethylsilylethoxymethoxy)xanthen-4-yl]-4-oxobutanoate
• CAS: 231621-44-6
• 化学式: C₃₁H₄₂O₈Si
• 分子量: 570.755
• InChiKey: BJDPAODLHKYBJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.97
• 重原子数：
  40.0
• 可旋转键数：
  15.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  89.52
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  1,8-dimethoxy-4-(ethyl-3'-formylpropanoate)-3-<2-(trimethylsilyl)ethoxymethoxy>-9H-xanthene-Δ^9,δ-butane 在 lithium aluminium tetrahydride 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 Angstroem MS 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 ((1S,2S)-5,7-Dimethoxy-6-oxo-2-triisopropylsilanyloxy-1,2-dihydro-6H-3,11-dioxa-cyclopenta[a]anthracen-1-yl)-acetaldehyde
  参考文献：
  名称：

  Total Synthesis of O-Methylsterigmatocystin Using N-Alkylnitrilium Salts and Carbonyl−Alkene Interconversion in a New Xanthone Synthesis

  摘要：

  A general strategy is described for the preparation of substituted xanthones and embodied in the preparation of (+/-)-O-methylsterigmatocystin (OMST), the most advanced, known intermediate in the biosynthesis of aflatoxin. The essential features of this approach are the reaction of N-alkylnitrilium salts with activated aromatic rings, and protection of the derived xanthones as their corresponding alkenyl xanthenes. The latter are readily synthesized by reaction with n-butyllithium and dehydration. The resulting stabilization of the xanthone nucleus enables a wide range of chemical modification reactions to be carried out, and a facile and unusual cleavage of the alkene with peracid restores the desired xanthone. Compatibility of these operations with the preparation of the sensitive dihydrobisfuran is exemplified in the synthesis of OMST.

  DOI：

  10.1021/jo990099w
• 作为产物：
  描述：

  2-氟-6-甲氧基苯腈 在 lithium aluminium tetrahydride 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 Angstroems MS 、 氯化锑(V) 、 水 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 88.0h， 生成 1,8-dimethoxy-4-(ethyl-3'-formylpropanoate)-3-<2-(trimethylsilyl)ethoxymethoxy>-9H-xanthene-Δ^9,δ-butane
  参考文献：
  名称：

  Total Synthesis of O-Methylsterigmatocystin Using N-Alkylnitrilium Salts and Carbonyl−Alkene Interconversion in a New Xanthone Synthesis

  摘要：

  A general strategy is described for the preparation of substituted xanthones and embodied in the preparation of (+/-)-O-methylsterigmatocystin (OMST), the most advanced, known intermediate in the biosynthesis of aflatoxin. The essential features of this approach are the reaction of N-alkylnitrilium salts with activated aromatic rings, and protection of the derived xanthones as their corresponding alkenyl xanthenes. The latter are readily synthesized by reaction with n-butyllithium and dehydration. The resulting stabilization of the xanthone nucleus enables a wide range of chemical modification reactions to be carried out, and a facile and unusual cleavage of the alkene with peracid restores the desired xanthone. Compatibility of these operations with the preparation of the sensitive dihydrobisfuran is exemplified in the synthesis of OMST.

  DOI：

  10.1021/jo990099w

文献信息

• Total Synthesis of <i>O</i>-Methylsterigmatocystin Using <i>N</i>-Alkylnitrilium Salts and Carbonyl−Alkene Interconversion in a New Xanthone Synthesis
  作者：Linda K. Casillas、Craig A. Townsend

  DOI：10.1021/jo990099w

  日期：1999.5.1

  A general strategy is described for the preparation of substituted xanthones and embodied in the preparation of (+/-)-O-methylsterigmatocystin (OMST), the most advanced, known intermediate in the biosynthesis of aflatoxin. The essential features of this approach are the reaction of N-alkylnitrilium salts with activated aromatic rings, and protection of the derived xanthones as their corresponding alkenyl xanthenes. The latter are readily synthesized by reaction with n-butyllithium and dehydration. The resulting stabilization of the xanthone nucleus enables a wide range of chemical modification reactions to be carried out, and a facile and unusual cleavage of the alkene with peracid restores the desired xanthone. Compatibility of these operations with the preparation of the sensitive dihydrobisfuran is exemplified in the synthesis of OMST.