(+)-Ethyl (2E)-2-<(3'S,5'R,6'S(1''S),7'S,9'S)-2'-aza-5'-<(tert-butyldimethylsilyl)oxy>-6'-<1''-cyclohexyl-1''-(tetrahydropyranyloxy)prop-2''-yn-3''-yl>-7'-(phenylsulfonyl)tricyclo<6.3.0.0^3',7'>undecanylidene>ethanoate | 163230-60-2

• 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: (+)-Ethyl (2E)-2-<(3'S,5'R,6'S(1''S),7'S,9'S)-2'-aza-5'-<(tert-butyldimethylsilyl)oxy>-6'-<1''-cyclohexyl-1''-(tetrahydropyranyloxy)prop-2''-yn-3''-yl>-7'-(phenylsulfonyl)tricyclo<6.3.0.0^3',7'>undecanylidene>ethanoate
• 英文别名: ethyl (2E)-2-[(1S,2R,3aS,7aS,8aS)-8a-(benzenesulfonyl)-2-[tert-butyl(dimethyl)silyl]oxy-1-[(3S)-3-cyclohexyl-3-(oxan-2-yloxy)prop-1-ynyl]-1,2,3,3a,6,7,7a,8-octahydrocyclopenta[b]pyrrolizin-5-ylidene]acetate
• CAS: 163230-60-2
• 化学式: C₄₀H₅₉NO₇SSi
• 分子量: 726.062
• InChiKey: XLNZJGOGYRMESY-MELNMWHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.79
• 重原子数：
  50
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  99.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (+)-Ethyl (2E)-2-<(3'S,5'R,6'S(1''S),7'S,9'S)-2'-aza-5'-<(tert-butyldimethylsilyl)oxy>-6'-<1''-cyclohexyl-1''-(tetrahydropyranyloxy)prop-2''-yn-3''-yl>-7'-(phenylsulfonyl)tricyclo<6.3.0.0^3',7'>undecanylidene>ethanoate 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以78%的产率得到(-)-Ethyl 2-<(1'S,3'S,5'R,6'S(1''S),7'S,9'S)-2'-aza-5'-<(tert-butyldimethylsilyl)oxy>-6'-<1''-cyclohexyl-1''-(tetrahydropyranyloxy)prop-2''-yn-3''-yl>-7'-(phenylsulfonyl)tricyclo<6.3.0.0^3',7'>undecanyl>ethanoate
  参考文献：
  名称：

  Syntheses Via Vinyl Sulfones. 58. A Triply Convergent Total Synthesis of a Symchiral Pyrrolidine-Fused Prostacyclin Analog

  摘要：

  The synthesis of symchiral 1-azatricyclo[6.3.0.0(2,6)]undeca-5-enyl prostaglandin I-2 analog 34 is reported. Construction of the tricyclic skeleton of 34 was accomplished in two steps by employing a triply convergent approach which utilized vinyl sulfone technology. Introduction of the heterocyclic subunit of 34 was achieved by an S(N)2'-thio-Claisen rearrangement which efficiently coupled a thiolactam moiety to a suitable allylic vinyl sulfone. Annulation of bicyclic vinyl sulfones 20, 23, and 29 was accomplished via a conjugate addition of Lithium acetylide 11 to the vinyl sulfone moieties, followed by an intramolecular S(N)2 displacement of a suitable nucleofuge. Competition between intramolecular carbon alkylation and beta-elimination of stabilized nitrogen anions from intermediate a-sulfonyl anions 20-i, 23-i, 29-i was discussed. Refunctionalization of the resulting tricyclic skeleton was accomplished by employing standard literature protocols. Compound 34 was found to be essentially inactive as an inhibitor of collagen-induced platelet aggregation, having an IC50 of > 10 mu M.

  DOI：

  10.1021/jo00114a016
• 作为产物：
  描述：

  (1S)-1-Cyclohexyl-1-(tetrahydropyran-2-yloxy)-2-propyne 、 (+)-Ethyl (2E)-2-<(3'S)-2'-aza-2'-<(1''S,4'R)-4''-<(tert-butyldimethylsilyl)oxy>-2''-(phenylsulfonyl)-2''-cyclopentenyl>-3'-(chloromethyl)cyclopentylidene>ethanoate 在 正丁基锂 作用下， 以 六甲基磷酰三胺 、 乙醚 、 正己烷 为溶剂， 以87%的产率得到(+)-Ethyl (2E)-2-<(3'S,5'R,6'S(1''S),7'S,9'S)-2'-aza-5'-<(tert-butyldimethylsilyl)oxy>-6'-<1''-cyclohexyl-1''-(tetrahydropyranyloxy)prop-2''-yn-3''-yl>-7'-(phenylsulfonyl)tricyclo<6.3.0.0^3',7'>undecanylidene>ethanoate
  参考文献：
  名称：

  Syntheses Via Vinyl Sulfones. 58. A Triply Convergent Total Synthesis of a Symchiral Pyrrolidine-Fused Prostacyclin Analog

  摘要：

  The synthesis of symchiral 1-azatricyclo[6.3.0.0(2,6)]undeca-5-enyl prostaglandin I-2 analog 34 is reported. Construction of the tricyclic skeleton of 34 was accomplished in two steps by employing a triply convergent approach which utilized vinyl sulfone technology. Introduction of the heterocyclic subunit of 34 was achieved by an S(N)2'-thio-Claisen rearrangement which efficiently coupled a thiolactam moiety to a suitable allylic vinyl sulfone. Annulation of bicyclic vinyl sulfones 20, 23, and 29 was accomplished via a conjugate addition of Lithium acetylide 11 to the vinyl sulfone moieties, followed by an intramolecular S(N)2 displacement of a suitable nucleofuge. Competition between intramolecular carbon alkylation and beta-elimination of stabilized nitrogen anions from intermediate a-sulfonyl anions 20-i, 23-i, 29-i was discussed. Refunctionalization of the resulting tricyclic skeleton was accomplished by employing standard literature protocols. Compound 34 was found to be essentially inactive as an inhibitor of collagen-induced platelet aggregation, having an IC50 of > 10 mu M.

  DOI：

  10.1021/jo00114a016