(R)-Methyl 5-Hydroxy-3-oxo-6-<(triisopropylsilyl)oxy>-hexanoate | 131702-25-5

• 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: (R)-Methyl 5-Hydroxy-3-oxo-6-<(triisopropylsilyl)oxy>-hexanoate
• 英文别名: methyl (5R)-5-hydroxy-3-oxo-6-tri(propan-2-yl)silyloxyhexanoate
• CAS: 131702-25-5
• 化学式: C₁₆H₃₂O₅Si
• 分子量: 332.513
• InChiKey: BNLYBZJFRXYASG-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  22
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-Methyl 5-Hydroxy-3-oxo-6-<(triisopropylsilyl)oxy>-hexanoate 在 sodium hydroxide 、 溶剂黄146 、 tetramethylammonium triacetoxyborohydride 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 24.0h， 生成 (4S,6S)-4-Hydroxy-6-<<(triisopropylsilyl)oxy>methyl>-2H-tetrahydropyran-2-one
  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：

  硅烷,[[(2S,3S)-3-(3-甲氧苯基)噁丙环基]甲氧基]三(1-甲基乙基)- 在 吡啶 、 二甲基硫 、 氨 、 lithium 、 臭氧 、 叔丁醇 、 苏丹红 作用下， 反应 13.75h， 生成 (R)-Methyl 5-Hydroxy-3-oxo-6-<(triisopropylsilyl)oxy>-hexanoate
  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

文献信息

• EVANS, DAVID A.;GAUCHET-PRUNET, JOELLE A.;CARREIRA, ERICK M.;CHARETTE, AN+, J. ORG. CHEM., 56,(1991) N, C. 741-750
  作者：EVANS, DAVID A.、GAUCHET-PRUNET, JOELLE A.、CARREIRA, ERICK M.、CHARETTE, AN+

  DOI：——

  日期：——