(2S,3R,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol | 140925-43-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2S,3R,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol
• 英文别名: (2S,3S,4R,5S,6S)-2,4,6-trimethyl-7-phenylmethoxyheptane-1,3,5-triol
• CAS: 140925-43-5
• 化学式: C₁₇H₂₈O₄
• 分子量: 296.407
• InChiKey: FSAMHBAOXMMZLC-QZLJAVCYSA-N

物化性质

• 沸点：
  468.5±45.0 °C(Predicted)
• 密度：
  1.091±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (S)-1-苄氧基-2-甲基戊烷-3-酮 在 tin(II) trifluoromethanesulfonate 、 B-hydroxydiisopinocampheylborane 、 三乙胺 、 间氯过氧苯甲酸 作用下， 反应 6.0h， 生成 (2S,3R,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).

  DOI：

  10.1021/ja00104a010

文献信息

• Studies in polypropionate synthesis: high π-face selectivity in syn aldol reactions of tin(II) enolates from (R)- and (S)-1-benzyloxy-2-methylpentan-3-one.
  作者：Ian Paterson、Richard D. Tillyer

  DOI：10.1016/s0040-4039(00)74697-1

  日期：1992.7

  Use of Sn(OTf)2/Et3N in the aldol reactions of the α-chiral ethyl ketones (R)- or (S)-1 with aldehydes leads to high stereoselectivity (90–95% ds, >-97% ee) for the 1,2-syn-2,4-syn adduct 7 or ent-7. This substrate-based selectivity is rationalised by chelation of the Sn(II) enolate.

  在α-手性乙基酮（R）-或（S）-1与醛的醛醇缩合反应中使用Sn（OTf）2 / Et 3 N会导致高立体选择性（90-95％ds，>-97％ee） ）对于1,2- syn -2,4- syn syn加合物7或ent - 7。通过对Sn（II）烯醇盐进行螯合可以合理地实现这种基于底物的选择性。
• Studies in polypropionate synthesis: a general approach to the synthesis of stereopentads
  作者：Ian Peterson、Julia A. Channon

  DOI：10.1016/s0040-4039(00)77718-5

  日期：1992.2
• Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one
  作者：Ian Paterson、Roger D. Norcross、Richard A. Ward、Pedro Romea、M. Anne Lister

  DOI：10.1021/ja00104a010

  日期：1994.12

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).