(9E,11R,12S,15R,16R,19S,20R,21E)-1,15,16,30-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-11,20-bis(2-trimethylsilylethoxymethoxy)triaconta-9,21-diene-12,19-diol | 193811-93-7

• 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: (9E,11R,12S,15R,16R,19S,20R,21E)-1,15,16,30-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-11,20-bis(2-trimethylsilylethoxymethoxy)triaconta-9,21-diene-12,19-diol
• CAS: 193811-93-7
• 化学式: C₆₆H₁₄₂O₁₀Si₆
• 分子量: 1264.36
• InChiKey: KBDHZUYKUFPIKO-IJOJEYQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.06
• 重原子数：
  82
• 可旋转键数：
  51
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  114
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  对甲苯磺酰氯 、 (9E,11R,12S,15R,16R,19S,20R,21E)-1,15,16,30-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-11,20-bis(2-trimethylsilylethoxymethoxy)triaconta-9,21-diene-12,19-diol 在 吡啶 作用下， 反应 12.0h， 以92%的产率得到(9E,21E,11R,12S,15R,16R,19S,20R)-1,11,20,30-tetrakis[(tert-butyldimethylsilyl)oxy]-11,20-bis[[2-(trimethylsilyl)ethoxy]methoxy]-9,21-triacontadiene-12,19-diol bis-p-toluenesulfonate
  参考文献：
  名称：

  Total Synthesis of the Annonaceous Acetogenin (+)-Asimicin. Development of a New Bidirectional Strategy

  摘要：

  The total synthesis of the Annonaceous acetogenin (+)-asimicin is described. The approach employs the (R)-alpha-OSEM allylic stannane 7 of >95% ee and the dialdehyde 8 obtained from (S,S)-diethyl tartrate. Addition of 7 to 8 in the presence of InCl3 afforded the bis-adduct 9 in 71% yield. Tosylation and treatment with TBAF led to the core bis-tetrahydrofuran intermediate, diol 11, in 78% yield. Mono tosylation (n-BuLi, TsCl, THF-DMSO) and subsequent hydrogenolysis with LiBEt3H gave alcohol 14. The iodide 15 was coupled with the higher-order vinylcyanocuprate to afford olefin 30. This was converted to diol 31 of high ee by the Sharpless protocol. This diol yielded the epoxide 33 via the mono-trisylate 32. Addition of (R)-lithio-2-(OTBS)-3-butyne in the presence of BF3 . OEt2 afforded the alcohol 34. The SEM derivative 35 was treated with TBAF, and the resulting alcohol was converted to the butenolide 38 by a sequence involving treatment with (CF3CO)(2)O, then Pd(PPh3)(4), CO, THF-H2O, and finally AgNO3/silica gel. Cleavage of the SEM protecting group with PPTS in ethanol afforded (+)-asimicin (39).

  DOI：

  10.1021/jo970423s
• 作为产物：
  描述：

  (E)-11-((tert-butyldimethylsilyl)oxy)undec-2-en-1-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (9E,11R,12S,15R,16R,19S,20R,21E)-1,15,16,30-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-11,20-bis(2-trimethylsilylethoxymethoxy)triaconta-9,21-diene-12,19-diol
  参考文献：
  名称：

  Total Synthesis of the Annonaceous Acetogenin (+)-Asimicin. Development of a New Bidirectional Strategy

  摘要：

  The total synthesis of the Annonaceous acetogenin (+)-asimicin is described. The approach employs the (R)-alpha-OSEM allylic stannane 7 of >95% ee and the dialdehyde 8 obtained from (S,S)-diethyl tartrate. Addition of 7 to 8 in the presence of InCl3 afforded the bis-adduct 9 in 71% yield. Tosylation and treatment with TBAF led to the core bis-tetrahydrofuran intermediate, diol 11, in 78% yield. Mono tosylation (n-BuLi, TsCl, THF-DMSO) and subsequent hydrogenolysis with LiBEt3H gave alcohol 14. The iodide 15 was coupled with the higher-order vinylcyanocuprate to afford olefin 30. This was converted to diol 31 of high ee by the Sharpless protocol. This diol yielded the epoxide 33 via the mono-trisylate 32. Addition of (R)-lithio-2-(OTBS)-3-butyne in the presence of BF3 . OEt2 afforded the alcohol 34. The SEM derivative 35 was treated with TBAF, and the resulting alcohol was converted to the butenolide 38 by a sequence involving treatment with (CF3CO)(2)O, then Pd(PPh3)(4), CO, THF-H2O, and finally AgNO3/silica gel. Cleavage of the SEM protecting group with PPTS in ethanol afforded (+)-asimicin (39).

  DOI：

  10.1021/jo970423s

文献信息

• Total Synthesis of the Annonaceous Acetogenin (+)-Asimicin. Development of a New Bidirectional Strategy
  作者：James A. Marshall、Kevin W. Hinkle

  DOI：10.1021/jo970423s

  日期：1997.8.1

  The total synthesis of the Annonaceous acetogenin (+)-asimicin is described. The approach employs the (R)-alpha-OSEM allylic stannane 7 of >95% ee and the dialdehyde 8 obtained from (S,S)-diethyl tartrate. Addition of 7 to 8 in the presence of InCl3 afforded the bis-adduct 9 in 71% yield. Tosylation and treatment with TBAF led to the core bis-tetrahydrofuran intermediate, diol 11, in 78% yield. Mono tosylation (n-BuLi, TsCl, THF-DMSO) and subsequent hydrogenolysis with LiBEt3H gave alcohol 14. The iodide 15 was coupled with the higher-order vinylcyanocuprate to afford olefin 30. This was converted to diol 31 of high ee by the Sharpless protocol. This diol yielded the epoxide 33 via the mono-trisylate 32. Addition of (R)-lithio-2-(OTBS)-3-butyne in the presence of BF3 . OEt2 afforded the alcohol 34. The SEM derivative 35 was treated with TBAF, and the resulting alcohol was converted to the butenolide 38 by a sequence involving treatment with (CF3CO)(2)O, then Pd(PPh3)(4), CO, THF-H2O, and finally AgNO3/silica gel. Cleavage of the SEM protecting group with PPTS in ethanol afforded (+)-asimicin (39).