(2R,6R,17R)-2-(tert-Butyl-dimethyl-silanyloxy)-17-(2-trimethylsilanyl-ethoxymethoxy)-17-{(2R,5R,2'R,5'R)-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-heptadec-3-yn-6-ol | 193812-16-7

• 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: (2R,6R,17R)-2-(tert-Butyl-dimethyl-silanyloxy)-17-(2-trimethylsilanyl-ethoxymethoxy)-17-{(2R,5R,2'R,5'R)-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-heptadec-3-yn-6-ol
• 英文别名: (2R,6R,17R)-2-[tert-butyl(dimethyl)silyl]oxy-17-(2-trimethylsilylethoxymethoxy)-17-[(2R,5R)-5-[(2R,5R)-5-[(1R)-1-(2-trimethylsilylethoxymethoxy)undecyl]oxolan-2-yl]oxolan-2-yl]heptadec-3-yn-6-ol
• CAS: 193812-16-7
• 化学式: C₅₄H₁₀₈O₈Si₃
• 分子量: 969.703
• InChiKey: WOURDZNEEVKJCY-ANMYAQNASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.07
• 重原子数：
  65
• 可旋转键数：
  39
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  84.8
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,6R,17R)-2-(tert-Butyl-dimethyl-silanyloxy)-17-(2-trimethylsilanyl-ethoxymethoxy)-17-{(2R,5R,2'R,5'R)-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-heptadec-3-yn-6-ol 在 2,6-二甲基吡啶 、 四(三苯基膦)钯 、 四丁基氟化铵 、 水 、 4-甲基苯磺酸吡啶 、 silica gel 、 silver nitrate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 38.03h， 生成 (5S)-3-[(2S,13R)-2,13-二羟基-13-[(2R,5R)-5-[(2R,5R)-5-[(1R)-1-羟基十一烷基]四氢呋喃-2-基]四氢呋喃-2-基]十三烷基]-5-甲基-5H-呋喃-2-酮
  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：

  (2R,5R,2'R,5'R)-5-[(R)-11-Iodo-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl 在 吡啶 、 potassium dioxotetrahydroxoosmate(VI) 、 hydroquinidine anthraquinone-1,4-diyl diether 、 K₂Fe₃(CN)6 、 三氟化硼乙醚 、 sodium hydride 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 36.5h， 生成 (2R,6R,17R)-2-(tert-Butyl-dimethyl-silanyloxy)-17-(2-trimethylsilanyl-ethoxymethoxy)-17-{(2R,5R,2'R,5'R)-5'-[(R)-1-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-octahydro-[2,2']bifuranyl-5-yl}-heptadec-3-yn-6-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).