(+)-methyl (2S,3S,4S,6R)-[6-(2-hydroxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate | 366454-74-2

• 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: (+)-methyl (2S,3S,4S,6R)-[6-(2-hydroxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate
• 英文别名: methyl [(2S,3S,4S,6R)-6-(2-hydroxyeth-1-yl)-3-methyl-4-[(triisopropylsilyl)oxy]-oxan-2-yl]acetate；methyl 2-[(2S,3S,4S,6R)-6-(2-hydroxyethyl)-3-methyl-4-tri(propan-2-yl)silyloxyoxan-2-yl]acetate
• CAS: 366454-74-2
• 化学式: C₂₀H₄₀O₅Si
• 分子量: 388.62
• InChiKey: GLVLODVOWJKDKY-RDGPPVDQSA-N

物化性质

• 沸点：
  426.2±30.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.29
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+)-methyl (2S,3S,4S,6R)-[6-(2-hydroxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate 在 2,6-二甲基吡啶 、 9-溴-9-硼杂双环-[3.3.1]壬烷 、 chromium dichloride 、 2,4,6-三氯苯甲酰氯 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 戴斯-马丁氧化剂 、 臭氧 、 三乙胺 、 nickel dichloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 84.0h， 生成 (1S,5S,7R,9R,10R,13S,15S,16S)-7,10-bis[(triethylsilyl)oxy]-4,17-dioxa-3,11-dioxo-6,6,9,16-tetramethyl-15-[(triisopropylsilyl)oxy]bicyclo[11.3.1]heptadecane-5-carboxaldehyde
  参考文献：
  名称：

  通过三羟基羧酸的选择性大环内酯化来完全合成海洋毒素聚卡维诺糖苷A。

  摘要：

  DOI：

  10.1021/ja011256n
• 作为产物：
  描述：

  (+)-methyl (2S,3S,4S,6R)-[6-(2-benzyloxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate 在 palladium on activated charcoal 咪唑 、 氢气 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (+)-methyl (2S,3S,4S,6R)-[6-(2-hydroxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate
  参考文献：
  名称：

  Total synthesis of a diastereomer of the marine natural product clavosolide A

  摘要：

  描述了对海绵代谢物克拉沃索尔A报告结构的首次总体合成，该合成采用Prins环化反应组装四氢呋喃核心，随后对侧链进行处理，进行二聚化，最后进行糖苷化反应。

  DOI：

  10.1039/b509757f

文献信息

• Stereoselective Synthesis of the Tetrahydropyran Core of Polycarvernoside A
  作者：Conor S. Barry、Nick Bushby、John R. Harding、Christine L. Willis

  DOI：10.1021/ol050840o

  日期：2005.6.1

  [reaction: see text] A concise and stereoselective synthesis of the tetrasubstituted tetrahydropyran core of polycavernoside A was achieved in 55% overall yield from 3-benzyloxypropanal. A stereoselective allyl transfer reaction was used in the synthesis of enol ether 18 followed by a TFA-mediated cyclization to create the three new asymmetric centers in the tetrahydropyran with complete stereocontrol in

  [反应：见正文]聚卡维诺糖苷A的四取代四氢吡喃核的简明和立体选择性合成以3-苄氧基丙醛的总收率为55％实现。在烯醇醚18的合成中使用立体选择性烯丙基转移反应，然后进行TFA介导的环化反应，在四氢吡喃中创建三个新的不对称中心，并在单锅法中实现完全的立体控制。
• Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga <i>Polycavernosa </i><i>t</i><i>sudai</i>
  作者：Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop、James D. White

  DOI：10.1021/jo0503862

  日期：2005.7.1

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.