(3S,5S,7S)-8-(tert-butyldiphenylsilyl)oxy-3,5-dihydroxy-4,4,7-trimethyloct-1-ene | 861119-26-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3S,5S,7S)-8-(tert-butyldiphenylsilyl)oxy-3,5-dihydroxy-4,4,7-trimethyloct-1-ene
• 英文别名: (3S,5S,7S)-8-[tert-butyl(diphenyl)silyl]oxy-4,4,7-trimethyloct-1-ene-3,5-diol
• CAS: 861119-26-8
• 化学式: C₂₇H₄₀O₃Si
• 分子量: 440.698
• InChiKey: VIWCYARDZRDTLJ-TUSQITKMSA-N

物化性质

• 沸点：
  515.8±50.0 °C(predicted)
• 密度：
  1.02±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,5S,7S)-8-(tert-butyldiphenylsilyl)oxy-3,5-dihydroxy-4,4,7-trimethyloct-1-ene 在 草酰氯 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (2S)-3-[(4S,6S)-6-ethenyl-2,2,5,5-tetramethyl-1,3-dioxan-4-yl]-2-methylpropanal
  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：

  D-(-)-泛酰内酯 在 lithium aluminium tetrahydride 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 tetramethylammonium triacetoxyborohydride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 75.67h， 生成 (3S,5S,7S)-8-(tert-butyldiphenylsilyl)oxy-3,5-dihydroxy-4,4,7-trimethyloct-1-ene
  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%.