dimethyl <1-(benzyloxy)cyclopent-2-en-4-yl>malonate | 143729-96-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl <1-(benzyloxy)cyclopent-2-en-4-yl>malonate
• 英文别名: dimethyl 2-[(1S,4R)-4-benzoyloxycyclopent-2-en-1-yl]propanedioate
• CAS: 143729-96-8
• 化学式: C₁₇H₁₈O₆
• 分子量: 318.326
• InChiKey: ODJXQRCGDJUVOM-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl <1-(benzyloxy)cyclopent-2-en-4-yl>malonate 在 N-[(2,4-二氯苯氧基)-甲氧基硫代膦酰]丙-2-胺 、 magnesium methanolate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 (S)-O-methylmandelate of dimethyl (1R,4S)-(1-hydroxycyclopent-2-en-4-yl)malonate
  参考文献：
  名称：

  A modular approach for ligand design for asymmetric allylic alkylations via enantioselective palladium-catalyzed ionizations

  摘要：

  A new class of ligands for asymmetric transition metal catalysis based on 2-(diphenylphosphino)benzoic acid was used in a mechanistically-defined palladium-catalyzed reaction in which enantiodifferentiation was the result of selective ionization of substrates derived from cis-2-cycloalkene-1,4-diols. By making rational, stepwise changes in the ligand structure, the structural requirements for good asymmetric induction were probed. The absolute stereochemistry of the products was found to be related to the chirality of the ligand in a predictable fashion. A mnemonic is given which allows one to predict the mode of ionization (R or S) solely on the basis of the stereochemistry of the variable chiral linker used to make the ligand.

  DOI：

  10.1021/ja00050a013
• 作为产物：
  描述：

  顺式-4-(苯甲酰氧基)-2-环戊烯基苯甲酸酯 、 丙二酸二甲酯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 JandeJEL-supported chiral biphosphane ligand 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 dimethyl <1-(benzyloxy)cyclopent-2-en-4-yl>malonate 、 dimethyl <1-(benzyloxy)cyclopent-2-en-4-yl>malonate
  参考文献：
  名称：

  Heterogeneous Pd-Catalyzed Asymmetric Allylic Substitution Using Resin-Supported Trost-Type Bisphosphane Ligands

  摘要：

  DOI：

  10.1002/1521-3773(20021018)41:20<3852::aid-anie3852>3.0.co;2-i

文献信息

• <i>C</i>₂-Symmetric Bisphosphinobioxazoline as a Chiral Ligand. Highly Enantioselective Palladium-Catalyzed Allylic Substitutions and Formation of <i>P</i>,<i>N</i>,<i>N</i>,<i>P</i> Tetradentate Palladium (II) Complexes
  作者：Sang-gi Lee、Chung Woo Lim、Choong Eui Song、Kwan Mook Kim、Chul Ho Jun

  DOI：10.1021/jo990126i

  日期：1999.6.1

  The C-2-symmetric bisphosphinobioxazoline [(S,S)-Phos-Biox] 4 was found to be a highly efficient chiral ligand for Pd-catalyzed enantioselective allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate and afforded enantioselectivities of up to 97% ee. Moderate enantioselectivities have been observed in Pd-catalyzed desymmetrizations of cis-1,4-bis(benzoyloxy)-cyclopent-2-ene (12) with dimethyl malonate (51-78% yield, 38-58% eel) and N-benzyl-N-methylamine (87% yield, 33% ee) nucleophiles and of biscarbamate 15 of cis-1,4-dihydroxycyclopent-2-ene (90% yield, 50% ee). A 1:1 molar mixture of(S,S)-Phos-Biox 4 with Pd(CH3CN)(2)Cl-2 and [(eta(3)-C3H5)PdCl](2) afforded the P,N,N,P-tetradentate Pd(II) complexes 19a and 19b, respectively. The structures of the complexes 19a,b were determined by X-ray analysis. The complex 19a also exhibited high enantioselectivity (86% yield, 92% ee) in allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate.
• Heterogeneous Pd-Catalyzed Asymmetric Allylic Substitution Using Resin-Supported Trost-Type Bisphosphane Ligands
  作者：Choong Eui Song、Jung Woon Yang、Eun Joo Roh、Sang-gi Lee、Jou Hyeon Ahn、Hogyu Han

  DOI：10.1002/1521-3773(20021018)41:20<3852::aid-anie3852>3.0.co;2-i

  日期：2002.10.18
• A modular approach for ligand design for asymmetric allylic alkylations via enantioselective palladium-catalyzed ionizations
  作者：Barry M. Trost、David L. Van Vranken、Carsten Bingel

  DOI：10.1021/ja00050a013

  日期：1992.11

  A new class of ligands for asymmetric transition metal catalysis based on 2-(diphenylphosphino)benzoic acid was used in a mechanistically-defined palladium-catalyzed reaction in which enantiodifferentiation was the result of selective ionization of substrates derived from cis-2-cycloalkene-1,4-diols. By making rational, stepwise changes in the ligand structure, the structural requirements for good asymmetric induction were probed. The absolute stereochemistry of the products was found to be related to the chirality of the ligand in a predictable fashion. A mnemonic is given which allows one to predict the mode of ionization (R or S) solely on the basis of the stereochemistry of the variable chiral linker used to make the ligand.