(1S,4R,1'S,6'S,9'S)-camphanic acid 1'-methoxycarbonyl-3',4'-dimethyl-bicyclo[4.3.0]oct-3'-en-9'-yl ester | 1207173-80-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: (1S,4R,1'S,6'S,9'S)-camphanic acid 1'-methoxycarbonyl-3',4'-dimethyl-bicyclo[4.3.0]oct-3'-en-9'-yl ester
• CAS: 1207173-80-5
• 化学式: C₂₃H₃₂O₆
• 分子量: 404.503
• InChiKey: RKVQMYMGRYOQRT-LHRGIAPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.72
• 重原子数：
  29.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  9-hydroxy-1-methoxycarbonyl-3,4-dimethyl-bicyclo[4.3.0]oct-3-ene 、 (1S)-(-)-莰烷酰氯 在 吡啶 作用下， 生成 (1S,4R,1'S,6'S,9'S)-camphanic acid 1'-methoxycarbonyl-3',4'-dimethyl-bicyclo[4.3.0]oct-3'-en-9'-yl ester 、 (1S,4R,1'R,6'R,9'R)-camphanic acid 1'-methoxycarbonyl-3',4'-dimethyl-bicyclo[4.3.0]oct-3'-en-9'-yl ester
  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

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

  DOI：10.2533/chimia.2011.231

  日期：——

  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.