[(1R,9S,16S)-12,13-dimethoxy-4-nitro-8-oxatetracyclo[7.7.1.02,7.010,15]heptadeca-2(7),3,5,10,12,14-hexaen-16-yl]-phenylmethanone | 1447951-98-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [(1R,9S,16S)-12,13-dimethoxy-4-nitro-8-oxatetracyclo[7.7.1.02,7.010,15]heptadeca-2(7),3,5,10,12,14-hexaen-16-yl]-phenylmethanone
• CAS: 1447951-98-5
• 化学式: C₂₅H₂₁NO₆
• 分子量: 431.445
• InChiKey: YFJNNUBXPQIHAG-XZOYJPPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4-nitro-2-vinylphenol 、 4,5-dimethoxy-2-(2-phenylethynyl)benzaldehyde 在 (S)-3,3'-bis(2,4,6-tri-iso-propylphenyl)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate 、 palladium diacetate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以89%的产率得到[(1R,9S,16S)-12,13-dimethoxy-4-nitro-8-oxatetracyclo[7.7.1.02,7.010,15]heptadeca-2(7),3,5,10,12,14-hexaen-16-yl]-phenylmethanone
  参考文献：
  名称：

  Asymmetric Cascade Annulation Based on Enantioselective Oxa-Diels–Alder Cycloaddition of in Situ Generated Isochromenyliums by Cooperative Binary Catalysis of Pd(OAc)₂ and (S)-Trip

  摘要：

  An asymmetric cascade annulation between 2-hydroxystyrenes and 2-alkynylbenaldehyes or 1-(2-alkynylphenyl)ketones has been established with good to excellent enantioselectivities (up to >99.5% ee), on the basis of an enantioselective oxa-Diels-Alder cycloaddition of in situ generated metallo-isochromenylium intermediates, by cooperative binary catalysis of Pd(OAc)(2) and (S)-Trip. The developed methodology is workable for a broad spectrum of substrates and shows great efficiency in establishing dense multiple chiral centers including quaternary carbons of variable bridged ring systems. The mechanism study suggests that (S)-Trip plays multiple roles in assembling the reactants and controlling the stereoselectivity.

  DOI：

  10.1021/ja405764p

文献信息

• Asymmetric Cascade Annulation Based on Enantioselective Oxa-Diels–Alder Cycloaddition of in Situ Generated Isochromenyliums by Cooperative Binary Catalysis of Pd(OAc)₂ and (<i>S</i>)-Trip
  作者：Shu-Yan Yu、Hao Zhang、Yang Gao、Lei Mo、Shaozhong Wang、Zhu-Jun Yao

  DOI：10.1021/ja405764p

  日期：2013.7.31

  An asymmetric cascade annulation between 2-hydroxystyrenes and 2-alkynylbenaldehyes or 1-(2-alkynylphenyl)ketones has been established with good to excellent enantioselectivities (up to >99.5% ee), on the basis of an enantioselective oxa-Diels-Alder cycloaddition of in situ generated metallo-isochromenylium intermediates, by cooperative binary catalysis of Pd(OAc)(2) and (S)-Trip. The developed methodology is workable for a broad spectrum of substrates and shows great efficiency in establishing dense multiple chiral centers including quaternary carbons of variable bridged ring systems. The mechanism study suggests that (S)-Trip plays multiple roles in assembling the reactants and controlling the stereoselectivity.