[(1S,3R)-3-[(1Z,3Z,5R,7R,8R,9E)-7-bis(prop-2-enoxy)phosphoryloxy-10-[(2S,3S)-3-ethyl-6-oxo-2,3-dihydropyran-2-yl]-5-(2-phenoxyacetyl)oxy-8-[2-(prop-2-enoxycarbonylamino)ethyl]-8-trimethylsilyloxydeca-1,3,9-trienyl]cyclohexyl] (6S)-6-methyloctanoate | 521274-37-3

• 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: [(1S,3R)-3-[(1Z,3Z,5R,7R,8R,9E)-7-bis(prop-2-enoxy)phosphoryloxy-10-[(2S,3S)-3-ethyl-6-oxo-2,3-dihydropyran-2-yl]-5-(2-phenoxyacetyl)oxy-8-[2-(prop-2-enoxycarbonylamino)ethyl]-8-trimethylsilyloxydeca-1,3,9-trienyl]cyclohexyl] (6S)-6-methyloctanoate
• CAS: 521274-37-3
• 化学式: C₅₅H₈₂NO₁₄PSi
• 分子量: 1040.31
• InChiKey: JAHTUVAROVGRIM-QKFXLNPCSA-N

物化性质

• 沸点：
  944.5±65.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.04
• 重原子数：
  72
• 可旋转键数：
  38
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  180
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  [(1S,3R)-3-[(1Z,3Z,5R,7R,8R,9E)-7-bis(prop-2-enoxy)phosphoryloxy-10-[(2S,3S)-3-ethyl-6-oxo-2,3-dihydropyran-2-yl]-5-(2-phenoxyacetyl)oxy-8-[2-(prop-2-enoxycarbonylamino)ethyl]-8-trimethylsilyloxydeca-1,3,9-trienyl]cyclohexyl] (6S)-6-methyloctanoate 在 erbium(III) triflate 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以68%的产率得到(1S,3R)-3-{(1Z,3Z,5R,7R,8R,9E)-8-(2-{[(allyloxyl)carbonyl]amino}ethyl)-7-{[bis(allyloxy)phosphoryl]oxy}-10-[(2S,3S)-3-ethyl-6-oxo-3,6-dihydro-2H-pyran-2-yl]-5-hydroxy-8-[(trimethylsilyl)oxy]deca-1,3,9-trienyl}cyclohexyl (6S)-6-methyloctanoate
  参考文献：
  名称：

  Total Synthesis of Leustroducsin B

  摘要：

  A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).

  DOI：

  10.1021/ja0340679
• 作为产物：
  描述：

  [(4R)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2,2-dimethyl-[1,3]dioxan-4-yl]methyl acetate 在 碳酸氢钠 吡啶 、 咪唑 、 四氮唑 、 lead(IV) acetate 、 titanium(IV) isopropylate 、 甲醇 、 三乙基硅烷 、 4-二甲氨基吡啶 、 manganese(IV) oxide 、 potassium osmate(VI) 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 ammonium cerium(IV) nitrate 、 三(2-氯乙基)胺 、 Br₂Cu^(1-)*Li⁽¹⁺⁾ 、 4 A molecular sieve 、 三氟甲磺酸二丁硼 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 四丁基氢氧化铵 、 水 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 potassium carbonate 、 溶剂黄146 、 triethylamine tris(hydrogen fluoride) 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 三苯基膦 、 zinc dibromide 、 potassium hexacyanoferrate(III) 、 锌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 叔丁醇 、 苯 为溶剂， 反应 191.01h， 生成 [(1S,3R)-3-[(1Z,3Z,5R,7R,8R,9E)-7-bis(prop-2-enoxy)phosphoryloxy-10-[(2S,3S)-3-ethyl-6-oxo-2,3-dihydropyran-2-yl]-5-(2-phenoxyacetyl)oxy-8-[2-(prop-2-enoxycarbonylamino)ethyl]-8-trimethylsilyloxydeca-1,3,9-trienyl]cyclohexyl] (6S)-6-methyloctanoate
  参考文献：
  名称：

  Total Synthesis of Leustroducsin B

  摘要：

  A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).

  DOI：

  10.1021/ja0340679

文献信息

• Total Synthesis of Leustroducsin B
  作者：Kousei Shimada、Yosuke Kaburagi、Tohru Fukuyama

  DOI：10.1021/ja0340679

  日期：2003.4.1

  A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).