[(2S,3S,4S,6R)-6-[[(3S,4R,6R,8R)-3,6,8-trihydroxy-4,7,7-trimethyldeca-1,9-dien-2-yl]methyl]-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetic acid | 366454-78-6

• 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: [(2S,3S,4S,6R)-6-[[(3S,4R,6R,8R)-3,6,8-trihydroxy-4,7,7-trimethyldeca-1,9-dien-2-yl]methyl]-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetic acid
• 英文别名: 2-[(2S,3S,4S,6R)-3-methyl-6-[(3S,4R,6R,8R)-3,6,8-trihydroxy-4,7,7-trimethyl-2-methylidenedec-9-enyl]-4-tri(propan-2-yl)silyloxyoxan-2-yl]acetic acid
• CAS: 366454-78-6
• 化学式: C₃₁H₅₈O₇Si
• 分子量: 570.883
• InChiKey: IKSMUCBGHNPFNF-ODMOVEOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.08
• 重原子数：
  39
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  116
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(2S,3S,4S,6R)-6-[[(3S,4R,6R,8R)-3,6,8-trihydroxy-4,7,7-trimethyldeca-1,9-dien-2-yl]methyl]-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetic acid 在 2,6-二甲基吡啶 、 2,4,6-三氯苯甲酰氯 、 臭氧 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 (1S,5S,7R,9R,10S,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：

  (2S)-3,3-dimethylbutane-1,2,4-triol 在 chromium dichloride 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 nickel dichloride 、 tetramethylammonium triacetoxyborohydride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 223.66h， 生成 [(2S,3S,4S,6R)-6-[[(3S,4R,6R,8R)-3,6,8-trihydroxy-4,7,7-trimethyldeca-1,9-dien-2-yl]methyl]-3-methyl-4-[(triisopropylsilyl)oxy]oxan-2-yl]acetic acid
  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

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%.