methyl [(2S,3S,4S,6R)-3-methyl-6-(prop-2-yn-1-yl)-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetate | 366454-75-3

• 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)-3-methyl-6-(prop-2-yn-1-yl)-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetate
• 英文别名: methyl 2-[(2S,3S,4S,6R)-3-methyl-6-prop-2-ynyl-4-tri(propan-2-yl)silyloxyoxan-2-yl]acetate
• CAS: 366454-75-3
• 化学式: C₂₁H₃₈O₄Si
• 分子量: 382.616
• InChiKey: ABLOFSCRCWIWNG-YRPNKDGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl [(2S,3S,4S,6R)-3-methyl-6-(prop-2-yn-1-yl)-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 、 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 101.0h， 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 (2Z,4S,5S,7R)-7,9-bis[(tert-butyldimethylsilyl)oxy]-4-methyl-5-[(triisopropylsilyl)oxy]non-2-enoate 在 potassium tert-butylate 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 29.0h， 生成 methyl [(2S,3S,4S,6R)-3-methyl-6-(prop-2-yn-1-yl)-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetate
  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

文献信息

• 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%.