dimethyl (E)-2-benzylideneglutarate | 1131452-11-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: dimethyl (E)-2-benzylideneglutarate
• 英文别名: dimethyl (E)-α-benzylideneglutarate；dimethyl (2E)-2-benzylidenepentanedioate
• CAS: 1131452-11-3
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: NNJKWTGUQOJVHI-ZRDIBKRKSA-N

物化性质

• 沸点：
  341.0±30.0 °C(predicted)
• 密度：
  1.129±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl (E)-2-benzylideneglutarate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R(Fc))-2-{(S(C))-1-N-methyl-N-[bis(4-trifluoromethylphenyl)phosphino]aminoethyl}-1-[(R(P))-(1-naphthyl)phenylphosphino]ferrocene 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、6.0 MPa 条件下， 反应 24.0h， 生成 dimethyl 2-benzylglutarate 、 dimethyl 2-benzylglutarate
  参考文献：
  名称：

  Asymmetric synthesis of chiral glutaric acid derivatives via Rh-catalyzed enantioselective hydrogenation

  摘要：

  The first Rh-catalyzed enantioselective hydrogenation of dimethyl 2-methyleneglutarate and its derivatives has been reported. For the hydrogenation of dimethyl 2-methyleneglutarate with a chiral ferrocene-based monodentate phosphoramidite ligand (FAPhos), good enantioselectivity (over 90% ee) with full conversions was achieved. In contrast, the hydrogenation of substrates bearing an aryl substituent at a methylene moiety proved to be more difficult, in which the best enantioselectivity, of up to 81% ee was obtained by the use of a P-stereogenic BoPhoz-type ligand. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.02.046
• 作为产物：
  描述：

  2-(羟基苯基甲基)-丙烯酸甲酯 在 吡啶 、 palladium diacetate 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 dimethyl (E)-2-benzylideneglutarate
  参考文献：
  名称：

  Asymmetric synthesis of chiral glutaric acid derivatives via Rh-catalyzed enantioselective hydrogenation

  摘要：

  The first Rh-catalyzed enantioselective hydrogenation of dimethyl 2-methyleneglutarate and its derivatives has been reported. For the hydrogenation of dimethyl 2-methyleneglutarate with a chiral ferrocene-based monodentate phosphoramidite ligand (FAPhos), good enantioselectivity (over 90% ee) with full conversions was achieved. In contrast, the hydrogenation of substrates bearing an aryl substituent at a methylene moiety proved to be more difficult, in which the best enantioselectivity, of up to 81% ee was obtained by the use of a P-stereogenic BoPhoz-type ligand. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.02.046

文献信息

• Ring-opening Bis(alkoxycarbonylation) Reaction of Methylenecyclopropanes Catalyzed by Palladium in the Presence of Copper(I) Salt
  作者：Takahiro Aratani、Yutaka Ukaji、Katsuhiko Inomata

  DOI：10.1246/cl.2009.46

  日期：2009.1.5

  A palladium-catalyzed ring-opening bis(alkoxycarbonylation) reaction of methylenecyclopropanes in the presence of copper(I) salt was achieved under normal pressure of carbon monoxide and oxygen to give the corresponding α-methyleneglutarates.

  在一氧化碳和氧气的常压下，在铜（I）盐的存在下，钯催化的亚甲基环丙烷的开环双（烷氧基羰基化）反应得到相应的α-亚甲基戊二酸。
• Asymmetric synthesis of chiral glutaric acid derivatives via Rh-catalyzed enantioselective hydrogenation
  作者：Zheng-Chao Duan、Xiang-Ping Hu、Jun Deng、Sai-Bo Yu、Dao-Yong Wang、Zhuo Zheng

  DOI：10.1016/j.tetasy.2009.02.046

  日期：2009.3

  The first Rh-catalyzed enantioselective hydrogenation of dimethyl 2-methyleneglutarate and its derivatives has been reported. For the hydrogenation of dimethyl 2-methyleneglutarate with a chiral ferrocene-based monodentate phosphoramidite ligand (FAPhos), good enantioselectivity (over 90% ee) with full conversions was achieved. In contrast, the hydrogenation of substrates bearing an aryl substituent at a methylene moiety proved to be more difficult, in which the best enantioselectivity, of up to 81% ee was obtained by the use of a P-stereogenic BoPhoz-type ligand. (C) 2009 Elsevier Ltd. All rights reserved.