(3R,5R,6S)-Methyl 3,5-Dihydroxy-6-<(triisopropylsilyl)oxy>heptanoate | 131702-39-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (3R,5R,6S)-Methyl 3,5-Dihydroxy-6-<(triisopropylsilyl)oxy>heptanoate
• 英文别名: methyl (3R,5R,6R)-3,5-dihydroxy-6-tri(propan-2-yl)silyloxyheptanoate
• CAS: 131702-39-1
• 化学式: C₁₇H₃₆O₅Si
• 分子量: 348.555
• InChiKey: KMZFLYZZRWJVHS-BZUAXINKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  三乙基氯硅烷 、 (3R,5R,6S)-Methyl 3,5-Dihydroxy-6-<(triisopropylsilyl)oxy>heptanoate 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以77%的产率得到(3R,5R,6R)-Methyl 3-<(Triethylsilyl)oxy>-5-hydroxy-6-<(triisopropylsilyl)oxy>heptanoate
  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：

  (2S,3R)-4-(3-Methoxyphenyl)-2-<(triisopropylsilyl)oxy>-3-butanol 在 吡啶 、 二甲基硫 、 氨 、 lithium 、 二异丁基氢化铝 、 臭氧 、 tetramethylammonium triacetoxyborohydride 、 苏丹红 作用下， 以 溶剂黄146 、 乙腈 为溶剂， 反应 32.25h， 生成 (3R,5R,6S)-Methyl 3,5-Dihydroxy-6-<(triisopropylsilyl)oxy>heptanoate
  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