E-2-(4-methoxybenzylidene)glutarate de dimethyle | 172101-77-8

• 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: E-2-(4-methoxybenzylidene)glutarate de dimethyle
• 英文别名: dimethyl (E)-2-(4-methoxybenzylidene)glutarate；dimethyl (E)-α-(4-methoxybenzylidene)glutarate；dimethyl (2E)-2-[(4-methoxyphenyl)methylidene]pentanedioate
• CAS: 172101-77-8
• 化学式: C₁₅H₁₈O₅
• 分子量: 278.305
• InChiKey: YIKVIHNOPVNOEC-ZRDIBKRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  E-2-(4-methoxybenzylidene)glutarate de dimethyle 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-(4-methoxybenzyl)glutarate 、 dimethyl 2-(4-methoxybenzyl)glutarate
  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：

  methyl 2-[hydroxy(4-methoxyphenyl)methyl]prop-2-enoate 在 吡啶 、 palladium diacetate 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 E-2-(4-methoxybenzylidene)glutarate de dimethyle
  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

• Lignanes. 18. Synthèse Totale et Confirmation de la Structure de l'Acide Mégacérotonique
  作者：Eric Brown、Robert Dhal、Nadine Papin

  DOI：10.1016/0040-4020(95)00836-w

  日期：1995.11

  Megacerotonic acid 1 has a highly exceptional structure, since it is probably the only γ-butyrolactone lignan in which the lactone ring is substituted by an aryl, an arylidene and a carboxy group. The structure of this lignan was confirmed by a racemic total synthesis which involved as key-steps a Stobbe condensation of the 3-arylglutaric ester 8 with p-anisaldehyde 9, and the hydroxylation at C-4

  大cetrooniconic acid 1具有非常优异的结构，因为它可能是唯一的内酯环被芳基，亚芳基和羧基取代的γ-丁内酯木脂素。该木脂素的结构通过外消旋的全合成得到证实，该合成涉及作为关键步骤的3-芳基戊二酸酯8与对茴香醛9的Stobbe缩合，以及中间体2,3-二取代戊二醛在C-4处的羟基化。酯14。
• 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.