(5S,6S)-6-{(E)-2-[(2R,4R,5R)-2-[4-(tert-Butyl-dimethyl-silanyloxy)-phenyl]-5-{(3Z,5Z)-(R)-2-hydroxy-6-[(1R,3S)-3-(4-methoxy-phenoxymethoxy)-cyclohexyl]-hexa-3,5-dienyl}-4-(2-trityloxy-ethyl)-[1,3]dioxolan-4-yl]-vinyl}-5-ethyl-5,6-dihydro-pyran-2-one | 521274-33-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: (5S,6S)-6-{(E)-2-[(2R,4R,5R)-2-[4-(tert-Butyl-dimethyl-silanyloxy)-phenyl]-5-{(3Z,5Z)-(R)-2-hydroxy-6-[(1R,3S)-3-(4-methoxy-phenoxymethoxy)-cyclohexyl]-hexa-3,5-dienyl}-4-(2-trityloxy-ethyl)-[1,3]dioxolan-4-yl]-vinyl}-5-ethyl-5,6-dihydro-pyran-2-one
• 英文别名: (2S,3S)-2-[(E)-2-[(2R,4R,5R)-2-[4-[tert-butyl(dimethyl)silyl]oxyphenyl]-5-[(2R,3Z,5Z)-2-hydroxy-6-[(1R,3S)-3-[(4-methoxyphenoxy)methoxy]cyclohexyl]hexa-3,5-dienyl]-4-(2-trityloxyethyl)-1,3-dioxolan-4-yl]ethenyl]-3-ethyl-2,3-dihydropyran-6-one
• CAS: 521274-33-9
• 化学式: C₆₅H₇₈O₁₀Si
• 分子量: 1047.41
• InChiKey: XWCYGKVUNPBJEX-XZJVXZSKSA-N

物化性质

• 沸点：
  988.5±65.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.17
• 重原子数：
  76
• 可旋转键数：
  24
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (5S,6S)-6-{(E)-2-[(2R,4R,5R)-2-[4-(tert-Butyl-dimethyl-silanyloxy)-phenyl]-5-{(3Z,5Z)-(R)-2-hydroxy-6-[(1R,3S)-3-(4-methoxy-phenoxymethoxy)-cyclohexyl]-hexa-3,5-dienyl}-4-(2-trityloxy-ethyl)-[1,3]dioxolan-4-yl]-vinyl}-5-ethyl-5,6-dihydro-pyran-2-one 在 吡啶 、 四氮唑 、 三乙基硅烷 、 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 、 三(2-氯乙基)胺 、 水 、 溶剂黄146 、 triethylamine tris(hydrogen fluoride) 、 N,N'-二环己基碳二亚胺 、 三苯基膦 、 zinc dibromide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 44.92h， 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
• 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 、 lead(IV) acetate 、 titanium(IV) isopropylate 、 甲醇 、 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 、 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 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 N,N-二异丙基乙胺 、 potassium hexacyanoferrate(III) 、 锌 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 、 叔丁醇 、 苯 为溶剂， 反应 146.09h， 生成 (5S,6S)-6-{(E)-2-[(2R,4R,5R)-2-[4-(tert-Butyl-dimethyl-silanyloxy)-phenyl]-5-{(3Z,5Z)-(R)-2-hydroxy-6-[(1R,3S)-3-(4-methoxy-phenoxymethoxy)-cyclohexyl]-hexa-3,5-dienyl}-4-(2-trityloxy-ethyl)-[1,3]dioxolan-4-yl]-vinyl}-5-ethyl-5,6-dihydro-pyran-2-one
  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).