[(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-(methoxymethoxy)-4,4,7-trimethyloct-1-en-3-yl] benzoate | 861119-89-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-(methoxymethoxy)-4,4,7-trimethyloct-1-en-3-yl] benzoate
• CAS: 861119-89-3
• 化学式: C₃₆H₄₈O₅Si
• 分子量: 588.86
• InChiKey: OGWHJKVURCCBGV-WDZQTAOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.02
• 重原子数：
  42
• 可旋转键数：
  17
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-(methoxymethoxy)-4,4,7-trimethyloct-1-en-3-yl] benzoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以73%的产率得到[(3R,5R,7R)-8-hydroxy-5-(methoxymethoxy)-4,4,7-trimethyloct-1-en-3-yl] benzoate
  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：

  (R)-3-(tert-butyldiphenylsilyloxy)-2-methylpropan-1-ol 在 Oxone 、 正丁基锂 、 samarium diiodide 、 三丁基膦 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 55.67h， 生成 [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-(methoxymethoxy)-4,4,7-trimethyloct-1-en-3-yl] benzoate
  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 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%.