(E)-(R)-11-(2-Trimethylsilanyl-ethoxymethoxy)-11-{(2R,5R,2'R,5'R)-5'-[(E)-(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undec-2-enyl]-octahydro-[2,2']bifuranyl-5-yl}-undec-9-en-1-ol | 193811-97-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: (E)-(R)-11-(2-Trimethylsilanyl-ethoxymethoxy)-11-{(2R,5R,2'R,5'R)-5'-[(E)-(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undec-2-enyl]-octahydro-[2,2']bifuranyl-5-yl}-undec-9-en-1-ol
• 英文别名: (E,11R)-11-(2-trimethylsilylethoxymethoxy)-11-[(2R,5R)-5-[(2R,5R)-5-[(E,1R)-1-(2-trimethylsilylethoxymethoxy)undec-2-enyl]oxolan-2-yl]oxolan-2-yl]undec-9-en-1-ol
• CAS: 193811-97-1
• 化学式: C₄₂H₈₂O₇Si₂
• 分子量: 755.28
• InChiKey: SQURSZSTICKJJI-RLTBCBHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.06
• 重原子数：
  51
• 可旋转键数：
  32
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (E)-(R)-11-(2-Trimethylsilanyl-ethoxymethoxy)-11-{(2R,5R,2'R,5'R)-5'-[(E)-(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undec-2-enyl]-octahydro-[2,2']bifuranyl-5-yl}-undec-9-en-1-ol 在 rhodium on alumina 咪唑 、 氢气 、 碘 、 三苯基膦 作用下， 以 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 、 苯 为溶剂， 反应 13.0h， 生成 (R)-12-(2-Trimethylsilanyl-ethoxymethoxy)-12-{(2R,5R,2'R,5'R)-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-dodecanenitrile
  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)-(R)-11-{(2R,5R,2'R,5'R)-5'-[(E)-(R)-11-Hydroxy-1-(2-trimethylsilanyl-ethoxymethoxy)-undec-2-enyl]-octahydro-[2,2']bifuranyl-5-yl}-11-(2-trimethylsilanyl-ethoxymethoxy)-undec-9-en-1-ol 在 正丁基锂 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 16.5h， 生成 (E)-(R)-11-(2-Trimethylsilanyl-ethoxymethoxy)-11-{(2R,5R,2'R,5'R)-5'-[(E)-(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undec-2-enyl]-octahydro-[2,2']bifuranyl-5-yl}-undec-9-en-1-ol
  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).