<3R,4S,5S>-3-methoxy-5-<(p-methoxybenzyl)oxy>-6,6-dimethyl-4-(triethylsiloxy)-7-(trimethylsiloxy)-7-octenyl pivalate | 131698-91-4

• 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,4S,5S>-3-methoxy-5-<(p-methoxybenzyl)oxy>-6,6-dimethyl-4-(triethylsiloxy)-7-(trimethylsiloxy)-7-octenyl pivalate
• 英文别名: [3R,4S,5S]-3-methoxy-5-[(p-methoxybenzyl)oxy]-6,6-dimethyl-4-(triethylsiloxy)-7-(trimethylsiloxy)-7-octenyl pivalate；[(3R,4S,5S)-3-methoxy-5-[(4-methoxyphenyl)methoxy]-6,6-dimethyl-4-triethylsilyloxy-7-trimethylsilyloxyoct-7-enyl] 2,2-dimethylpropanoate
• CAS: 131698-91-4
• 化学式: C₃₃H₆₀O₇Si₂
• 分子量: 625.006
• InChiKey: SIFVEEUDIQWHDU-DYIKCSJPSA-N

物化性质

• 沸点：
  589.5±50.0 °C(predicted)
• 密度：
  0.978±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.36
• 重原子数：
  42.0
• 可旋转键数：
  19.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  <3R,4S,5S>-3-methoxy-5-<(p-methoxybenzyl)oxy>-6,6-dimethyl-4-(triethylsiloxy)-7-(trimethylsiloxy)-7-octenyl pivalate 在 三氟化硼乙醚 、 氢氟酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 11.5h， 生成 <3R,3(2S,3S,5S,7R,8R,9S)>-3-<9-hydroxy-3-<(p-methoxybenzyl)oxy>-4,4,8-trimethyl-7-vinyl-1,6-dioxaspiro<4.5>dec-2-yl>-3-methoxypropyl pivalate
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024
• 作为产物：
  描述：

  (3R,4S,5S)-3-Methoxy-5-(4-methoxy-benzyloxy)-6,6,7-trimethyl-4-triethylsilanyloxy-oct-7-enal 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 四氧化锇 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 40.75h， 生成 <3R,4S,5S>-3-methoxy-5-<(p-methoxybenzyl)oxy>-6,6-dimethyl-4-(triethylsiloxy)-7-(trimethylsiloxy)-7-octenyl pivalate
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024

文献信息

• Asymmetric synthesis of calyculin A. 1. The C1-C25 spiroketal fragment
  作者：David A. Evans、James R. Gage

  DOI：10.1021/jo00033a009

  日期：1992.3

  An asymmetric synthesis of the C1-C25 portion of calyculin A has been developed.