tert-butyl (8R,13S,14S,17S)-17-hydroxy-3-methoxy-6,7,8,12,14,15,16,17-octahydro-13H-cyclopenta[a]phenanthrene-13-carboxylate | 1207173-77-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: tert-butyl (8R,13S,14S,17S)-17-hydroxy-3-methoxy-6,7,8,12,14,15,16,17-octahydro-13H-cyclopenta[a]phenanthrene-13-carboxylate
• CAS: 1207173-77-0
• 化学式: C₂₃H₃₀O₄
• 分子量: 370.489
• InChiKey: RPSKEAZXZCCMFV-MXBUBSDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  27.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (8R,13S,14S,17S)-17-hydroxy-3-methoxy-6,7,8,12,14,15,16,17-octahydro-13H-cyclopenta[a]phenanthrene-13-carboxylate 、 (1S)-(-)-莰烷酰氯 在 吡啶 作用下， 生成 Camphanic Acid Ester ent-14
  参考文献：
  名称：

  Enantioselective Diels-Alder Reactions of Unsaturated ?-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes

  摘要：

  We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt(2))(2)(PNNP)](PF(6))(2), formed in situ from [RuCl(2)(PNNP)] and (Et(3)O)PF(6)(2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

  DOI：

  10.2533/chimia.2011.231
• 作为产物：
  描述：

  (8R,13S,14S)-13-tert-butoxycarbonyl-3-methoxy-7,8,12,13,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17(14H)-one 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 tert-butyl (8R,13S,14S,17S)-17-hydroxy-3-methoxy-6,7,8,12,14,15,16,17-octahydro-13H-cyclopenta[a]phenanthrene-13-carboxylate
  参考文献：
  名称：

  Enantioselective Diels-Alder Reactions of Unsaturated ?-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes

  摘要：

  We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt(2))(2)(PNNP)](PF(6))(2), formed in situ from [RuCl(2)(PNNP)] and (Et(3)O)PF(6)(2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

  DOI：

  10.2533/chimia.2011.231