(2S,3S,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol | 140925-44-6

• 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,3S,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol
• 英文别名: (2S,3S,4R,5R,6S)-2,4,6-trimethyl-7-phenylmethoxyheptane-1,3,5-triol
• CAS: 140925-44-6
• 化学式: C₁₇H₂₈O₄
• 分子量: 296.407
• InChiKey: FSAMHBAOXMMZLC-GFISCPRKSA-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

• 作为反应物：
  描述：

  (2S,3S,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol 在 palladium on activated charcoal 、 镍 盐酸 、 4-二甲氨基吡啶 、 sodium periodate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 lithium diethylamide 、 sodium perchlorate 、 氢气 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 镍 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 77.5h， 生成 (2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-9,11-dihydroxy-3,5-(isopropylidenedioxy)-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide
  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
• 作为产物：
  描述：

  (S)-1-苄氧基-2-甲基戊烷-3-酮 在 tin(II) trifluoromethanesulfonate 、 三乙胺 、 间氯过氧苯甲酸 、 (+)-二异松蒎烯基硼烷 作用下， 生成 (2S,3S,4R,5R,6S)-7-(benzyloxy)-2,4,6-trimethyl-1,3,5-heptanetriol
  参考文献：
  名称：

  Substrate-Controlled Aldol Reactions of Chiral Ethyl Ketones: Application to the Total Synthesis of Oleandomycin

  摘要：

  DOI：

  10.1021/ja00087a068

文献信息

• Stereocontrolled Synthesis of Polypropionate Fragments based on a Building Block Assembly Strategy using Lithiation-Borylation Methodologies
  作者：Alba Millán、Pablo D. Grigol Martinez、Varinder K. Aggarwal

  DOI：10.1002/chem.201704946

  日期：2018.1.12

  alternative strategy is presented in which stereochemically predefined building blocks, bearing appropriate functionality, are coupled together using a lithiation‐borylation methodology with complete stereocontrol. The building blocks comprise lithiated carbamates acting as donors, and boronic esters acting as acceptors. The acceptor building blocks contain β‐hydroxyl groups masked as silyl groups to avoid elimination

  聚丙烯酸酯是自然界中重要的结构基序，通常通过迭代的羟醛或丁酰化方法制备。在这里，提出了一种替代策略，其中采用具有完全立体控制的锂化-硼化方法，将具有适当功能的立体化学预定义的构建基块耦合在一起。组成部分包括充当供体的锂化氨基甲酸酯和充当受体的硼酸酯。受体结构单元包含被掩蔽为甲硅烷基的β-羟基，以避免消除硼酸酯中间体。随后，硼和甲硅烷基部分的氧化可提供一系列具有完全立体化学控制的聚丙烯酸酯片段，包括具有挑战性的合成抗-抗 异构体。
• Studies in macrolide synthesis: A stereocontrolled synthesis of a (9S)-macrolide intermediate for oleandomycin using chiral boron reagents.
  作者：Ian Paterson、M.Anne Lister、Roger D. Norcross

  DOI：10.1016/s0040-4039(00)91728-3

  日期：1992.3

  The (9S)-macrolide 1 (P = TBS) was prepared in 14 steps (5% yield) with 63% overall ds starting from the ethyl ketone (S)-2. The C1-C7 and C8-C13 segments, 3 and 4, were obtained via boron enolate aldol reactions mediated by (+)- and (-)-(Ipc)2BOTf, respectively.
• Substrate-Controlled Aldol Reactions of Chiral Ethyl Ketones: Application to the Total Synthesis of Oleandomycin
  作者：Ian Paterson、Richard A. Ward、Pedro Romea、Roger D. Norcross

  DOI：10.1021/ja00087a068

  日期：1994.4
• 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).