methyl [(2S,3S,4S,6R)-6-(carboxymethyl)-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetate | 366455-02-9

• 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-(carboxymethyl)-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetate
• 英文别名: methyl 2-[(2S,3S,4S,6S)-3-methyl-6-(2-oxoethyl)-4-tri(propan-2-yl)silyloxyoxan-2-yl]acetate
• CAS: 366455-02-9
• 化学式: C₂₀H₃₈O₅Si
• 分子量: 386.604
• InChiKey: ZMOBBILNJCOWLN-RDGPPVDQSA-N

物化性质

• 沸点：
  421.2±30.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl [(2S,3S,4S,6R)-6-(carboxymethyl)-3-methyl-4-[(triisopropylsilyl)oxy]oxan-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 、 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 103.0h， 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：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  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%.

  DOI：

  10.1021/jo0503862
• 作为产物：
  描述：

  (+)-methyl (2S,3S,4S,6R)-[6-(2-benzyloxyethyl)-4-hydroxy-3-methyltetrahydropyran-2-yl]-acetate 在 咪唑 、 戴斯-马丁氧化剂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 methyl [(2S,3S,4S,6R)-6-(carboxymethyl)-3-methyl-4-[(triisopropylsilyl)oxy]oxan-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

• Total Synthesis of the Marine Natural Product (−)-Clavosolide A
  作者：Conor S. Barry、Jon D. Elsworth、Peter T. Seden、Nick Bushby、John R. Harding、Roger W. Alder、Christine L. Willis

  DOI：10.1021/ol0611705

  日期：2006.7.1

  [Structure: see text] The total synthesis of the marine metabolite clavosolide A is reported which confirms the structure and absolute configuration of the natural product as the symmetrical diolide glycosylated by permethylated D-xylose moieties, 2.

  [结构：见正文]据报道，海洋代谢产物clavosolide A的总合成证实了天然产物的结构和绝对构型，该产物为被过甲基化的D-木糖部分糖基化的对称二元醇。
• Total Synthesis of the Marine Toxin Polycavernoside A via Selective Macrolactonization of a Trihydroxy Carboxylic Acid
  作者：James D. White、Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop

  DOI：10.1021/ja011256n

  日期：2001.9.1
• 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%.
• Total synthesis of a diastereomer of the marine natural product clavosolide A
  作者：Conor S Barry、Nick Bushby、Jonathan P. H. Charmant、Jon D. Elsworth、John R. Harding、Christine L. Willis

  DOI：10.1039/b509757f

  日期：——

  The first total synthesis of the reported structure of the sponge metabolite clavosolide A is described using a Prins cyclisation to assemble the tetrahydropyran core followed by manipulation of the side-chain, dimerisation and finally glycosidation.

  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。