Dimethyl 3,8-Dioxo-5-<(triethylsilyl)oxy>decanedioate | 131702-45-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: Dimethyl 3,8-Dioxo-5-<(triethylsilyl)oxy>decanedioate
• 英文别名: dimethyl 3,8-dioxo-5-triethylsilyloxydecanedioate
• CAS: 131702-45-9
• 化学式: C₁₈H₃₂O₇Si
• 分子量: 388.533
• InChiKey: PRTSPGAAUWAPRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  26
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  96
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Dimethyl 3,8-Dioxo-5-<(triethylsilyl)oxy>decanedioate 在 氟化氢吡啶 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 1.0h， 生成 5-Hydroxy-3,8-dioxo-decanedioic acid dimethyl ester
  参考文献：
  名称：

  Synthesis of 1,3-diol synthons from epoxy aromatic precursors: an approach to the construction of polyacetate-derived natural products

  摘要：

  The identification of stereoregular polyol subunits within polyacetate-derived natural products such as bryostatin 1 and amphotericin B has led to the convergent synthesis of six- and seven-carbon 1,3-diol fragments in high yields and stereoselectivities. This plan relies upon the enantioselective asymmetric epoxidation/kinetic resolution of cinnamyl alcohols and the use of meta-substituted anisyl rings as masked beta-keto ester synthons. Birch reduction[GRAPHICS]of 9 (R = Si(i)Pr3) followed by ozonolysis afforded the hydroxyl keto ester 11 in 66% overall yield. Anti-selective beta-selective beta-hydroxy ketone reduction employing Me4NBH(OAc)3 afforded 12 in 93% yield and 13:1 diastereoselectivity while syn-selective reduction with Et2BOMe/NaBH4 gave 13 in 82% yield and 15:1 diastereoselectivity. An analogous sequence of reactions provided 25 and 26 from epoxy alcohol 18. Epoxy aromatic alcohol 17 (R = H) was easily converted to 18 (93% yield, > 99:1) by Mitsunobu inversion followed by methanolysis. This reaction sequence provides access to all stereoisomers of 3,5,6-trihydroxyhexanoic acid hepatonic acids which should be useful chiral subunits of polyacetate-derived natural products such as amphotericin and bryostatin.

  DOI：

  10.1021/jo00002a048
• 作为产物：
  描述：

  6,7-Dimethoxy-2-<(triethylsilyl)oxy>tetralin 在 palladium on activated charcoal 氨 、 氢气 、 lithium 、 臭氧 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 3.25h， 生成 Dimethyl 3,8-Dioxo-5-<(triethylsilyl)oxy>decanedioate
  参考文献：
  名称：

  Synthesis of 1,3-diol synthons from epoxy aromatic precursors: an approach to the construction of polyacetate-derived natural products

  摘要：

  The identification of stereoregular polyol subunits within polyacetate-derived natural products such as bryostatin 1 and amphotericin B has led to the convergent synthesis of six- and seven-carbon 1,3-diol fragments in high yields and stereoselectivities. This plan relies upon the enantioselective asymmetric epoxidation/kinetic resolution of cinnamyl alcohols and the use of meta-substituted anisyl rings as masked beta-keto ester synthons. Birch reduction[GRAPHICS]of 9 (R = Si(i)Pr3) followed by ozonolysis afforded the hydroxyl keto ester 11 in 66% overall yield. Anti-selective beta-selective beta-hydroxy ketone reduction employing Me4NBH(OAc)3 afforded 12 in 93% yield and 13:1 diastereoselectivity while syn-selective reduction with Et2BOMe/NaBH4 gave 13 in 82% yield and 15:1 diastereoselectivity. An analogous sequence of reactions provided 25 and 26 from epoxy alcohol 18. Epoxy aromatic alcohol 17 (R = H) was easily converted to 18 (93% yield, > 99:1) by Mitsunobu inversion followed by methanolysis. This reaction sequence provides access to all stereoisomers of 3,5,6-trihydroxyhexanoic acid hepatonic acids which should be useful chiral subunits of polyacetate-derived natural products such as amphotericin and bryostatin.

  DOI：

  10.1021/jo00002a048