((1S,3S,5R)-3-Methoxycarbonylmethyl-2,8-dioxa-bicyclo[3.2.1]oct-1-yl)-acetic acid methyl ester | 131702-48-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: ((1S,3S,5R)-3-Methoxycarbonylmethyl-2,8-dioxa-bicyclo[3.2.1]oct-1-yl)-acetic acid methyl ester
• 英文别名: methyl 2-[(1S,3S,5R)-1-(2-methoxy-2-oxoethyl)-2,8-dioxabicyclo[3.2.1]octan-3-yl]acetate
• CAS: 131702-48-2
• 化学式: C₁₂H₁₈O₆
• 分子量: 258.271
• InChiKey: XBTRJNVKDIZRLQ-PTRXPTGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  Dimethyl 3,8-Dioxo-5-<(triethylsilyl)oxy>decanedioate 在 4-甲基苯磺酸吡啶 、 氟化氢吡啶 、 tetramethylammonium triacetoxyborohydride 作用下， 以 四氢呋喃 、 吡啶 、 乙醇 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 29.0h， 生成 ((1S,3S,5R)-3-Methoxycarbonylmethyl-2,8-dioxa-bicyclo[3.2.1]oct-1-yl)-acetic acid methyl 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

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：——