3,4-dimethoxy-1-ethoxycarbonyl-9-oxo-bicyclo[4.3.0]oct-3-ene | 1207173-83-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,4-dimethoxy-1-ethoxycarbonyl-9-oxo-bicyclo[4.3.0]oct-3-ene
• 英文别名: ethyl (3aS,7aS)-5,6-dimethoxy-3-oxo-2,4,7,7a-tetrahydro-1H-indene-3a-carboxylate
• CAS: 1207173-83-8
• 化学式: C₁₄H₂₀O₅
• 分子量: 268.31
• InChiKey: IZKIHIYMAUCDNF-XPTSAGLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2,3-二甲氧基-1,3-丁二烯 、 5-氧代环戊烯-1-羧酸乙酯 在 copper(I) trifluoromethanesulfonate benzene 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 3,4-dimethoxy-1-ethoxycarbonyl-9-oxo-bicyclo[4.3.0]oct-3-ene
  参考文献：
  名称：

  Asymmetric Diels−Alder Reactions of Unsaturated β-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes

  摘要：

  Cyclic alpha-unsaturated beta-ketoesters undergo cycloaddition with di- and trisubstituted butadienes to give tetrahydro-1-indanone derivatives with up to 93% ee in the presence of a ruthenium catalyst formed by activation of [RuCl(2)(PNNP)] with (Et(3)P)PF(6) (2 equiv) (PNNP = (1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine). The protocol has been used to prepare the estrone derivative (8R, 13S, 14S)-13-tert-butoxycarbonyl-3-methoxy-7,8,1 2,13,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17(14H)-one as a single diastereoisomer with 85% yield and 99% ee after one crystallization step. Its absolute configuration, which has been determined by X-ray diffraction after reduction to the alcohol and esterification with camphanic chloride, is in agreement with the attack of the diene onto the open enantioface of the beta-keto ester (O-O) in the ruthenium complex [Ru(O-O)(PNNP)](2+), whose X-ray structure has been determined.

  DOI：

  10.1021/ja910039e

文献信息

• Asymmetric Diels−Alder Reactions of Unsaturated β-Ketoesters Catalyzed by Chiral Ruthenium PNNP Complexes
  作者：Christoph Schotes、Antonio Mezzetti

  DOI：10.1021/ja910039e

  日期：2010.3.24

  Cyclic alpha-unsaturated beta-ketoesters undergo cycloaddition with di- and trisubstituted butadienes to give tetrahydro-1-indanone derivatives with up to 93% ee in the presence of a ruthenium catalyst formed by activation of [RuCl(2)(PNNP)] with (Et(3)P)PF(6) (2 equiv) (PNNP = (1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine). The protocol has been used to prepare the estrone derivative (8R, 13S, 14S)-13-tert-butoxycarbonyl-3-methoxy-7,8,1 2,13,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17(14H)-one as a single diastereoisomer with 85% yield and 99% ee after one crystallization step. Its absolute configuration, which has been determined by X-ray diffraction after reduction to the alcohol and esterification with camphanic chloride, is in agreement with the attack of the diene onto the open enantioface of the beta-keto ester (O-O) in the ruthenium complex [Ru(O-O)(PNNP)](2+), whose X-ray structure has been determined.