(3R',4S,4'S,5'R)-4-isopropyl-3-<(5'-methyl-2'-N,3'-diphenylisoxazolidine-4'-yl)carbonyl>-1,3-oxazolidin-2-one | 173778-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (3R',4S,4'S,5'R)-4-isopropyl-3-<(5'-methyl-2'-N,3'-diphenylisoxazolidine-4'-yl)carbonyl>-1,3-oxazolidin-2-one
• 英文别名: (+)-(3'R,4S,4'S,5'R)-4-isopropyl-3-((5'-methyl-2'-N,3'-diphenylisoxazolidin-4'-yl)carbonyl)-1,3-oxazolidin-2-one；(4S)-3-[(3R,4S,5R)-5-methyl-2,3-diphenyl-1,2-oxazolidine-4-carbonyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 173778-56-8
• 化学式: C₂₃H₂₆N₂O₄
• 分子量: 394.47
• InChiKey: PPILLHTYDXUPFO-OTNPHJDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  titanium(IV)isopropoxide 、 (3R',4S,4'S,5'R)-4-isopropyl-3-<(5'-methyl-2'-N,3'-diphenylisoxazolidine-4'-yl)carbonyl>-1,3-oxazolidin-2-one 在 异丙醇 作用下， 以 甲苯 为溶剂， 反应 5.0h， 生成 (3R,4S,5R)-4-isoxazolidinecarboxylic acid, 5-methyl-2,3-diphenyl-, isopropyl ester
  参考文献：
  名称：

  Control of Diastereo- and Enantioselectivity in Metal-Catalyzed 1,3-Dipolar Cycloaddition Reactions of Nitrones with Alkenes. Experimental and Theoretical Investigations

  摘要：

  The scopes and limitations of the catalytic effects of achiral and chiral Mg(II) and Cu(II) complexes on the stereochemistry of the 1,3-dipolar cycloaddition reaction of nitrones with alkenes have been investigated. A remarkably high degree of endo-selectivity (endo/exo > 20) is induced in the 1,3-dipolar cycloaddition reaction by the presence of a catalytic amount of, especially, a Mg(II)-phenanthroline complex. The diastereochemical assignment of the product is confirmed by an X-ray crystallographic determination of the structure of the exo-isoxazolidine. By the reaction of an alkene bearing a chiral auxiliary, with different nitrones and a catalytic amount of the Mg(II)-phenanthroline complex, one of four possible diastereomers of the isoxazolidines is exclusively formed. The absolute stereochemistry of this product is also assigned by an X-ray crystallographic investigation. The presence of a catalytic amount of a chiral Mg(II)-bisoxazoline complex in the 1,3-dipolar cycloaddition reaction leads to high endo-selectivity and occasionally with an ee > 80%. The reaction mechanism of the Mg(II)-catalyzed reaction is discussed on the basis of the experimental results and semiempirical quantum chemical calculations. The calculations are used to account for the catalytic effect of the Mg(II)-ligand complexes and to determine transition state energies for both the uncatalyzed and Mg(II)-ligand-catalyzed reactions.

  DOI：

  10.1021/jo951204e
• 作为产物：
  描述：

  (4S)-N-巴豆酰基-4-异丙基-2-恶唑烷酮 、 C,N-diphenylnitrone 在 Mg(II)-phenanthroline 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 生成 (3R',4S,4'S,5'R)-4-isopropyl-3-<(5'-methyl-2'-N,3'-diphenylisoxazolidine-4'-yl)carbonyl>-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Control of Diastereo- and Enantioselectivity in Metal-Catalyzed 1,3-Dipolar Cycloaddition Reactions of Nitrones with Alkenes. Experimental and Theoretical Investigations

  摘要：

  The scopes and limitations of the catalytic effects of achiral and chiral Mg(II) and Cu(II) complexes on the stereochemistry of the 1,3-dipolar cycloaddition reaction of nitrones with alkenes have been investigated. A remarkably high degree of endo-selectivity (endo/exo > 20) is induced in the 1,3-dipolar cycloaddition reaction by the presence of a catalytic amount of, especially, a Mg(II)-phenanthroline complex. The diastereochemical assignment of the product is confirmed by an X-ray crystallographic determination of the structure of the exo-isoxazolidine. By the reaction of an alkene bearing a chiral auxiliary, with different nitrones and a catalytic amount of the Mg(II)-phenanthroline complex, one of four possible diastereomers of the isoxazolidines is exclusively formed. The absolute stereochemistry of this product is also assigned by an X-ray crystallographic investigation. The presence of a catalytic amount of a chiral Mg(II)-bisoxazoline complex in the 1,3-dipolar cycloaddition reaction leads to high endo-selectivity and occasionally with an ee > 80%. The reaction mechanism of the Mg(II)-catalyzed reaction is discussed on the basis of the experimental results and semiempirical quantum chemical calculations. The calculations are used to account for the catalytic effect of the Mg(II)-ligand complexes and to determine transition state energies for both the uncatalyzed and Mg(II)-ligand-catalyzed reactions.

  DOI：

  10.1021/jo951204e

文献信息

• Improvement of TADDOLate−TiCl₂-Catalyzed 1,3-Dipolar Nitrone Cycloaddition Reactions by Substitution of the Oxazolidinone Auxiliary of the Alkene with Succinimide
  作者：Kim B. Jensen、Kurt V. Gothelf、Rita G. Hazell、Karl Anker Jørgensen

  DOI：10.1021/jo962214y

  日期：1997.4.1

  tested as catalysts for the 1,3-dipolar cycloaddition reactions, and the most successful catalyst was applied (5 mol %) in a series of reactions between two different alkenoylsuccinimides and three different nitrones. The crude products containing an N-acylsuccinimide moiety were converted directly into the corresponding carboxamides upon treatment with hydrazine. The 1,3-dipolar cycloaddition reactions

  使用琥珀酰亚胺作为α，β-不饱和羰基部分的新辅助剂，描述了金属催化的无环硝酮与α，β-不饱和羰基化合物的不对称1,3-偶极环加成反应的显着改进。在没有催化剂的情况下，N-巴豆酰琥珀酰亚胺与C，N-二苯基硝酮反应生成内异异唑烷，而在10 mol％TiCl（2）（i-PrO）（2）的存在下，获得了外切产物。已经测试了四种不同的TiCl（2）-TADDOLate配合物作为1,3-偶极环加成反应的催化剂，最成功的催化剂（5 mol％）被应用在两种不同的烯基琥珀酰亚胺和三种不同的硝酮之间的一系列反应中。在用肼处理后，将含有N-酰基琥珀酰亚胺部分的粗产物直接转化为相应的羧酰胺。1,3-偶极环加成反应以高的exo-选择度进行，通常> 90％de，与以前使用恶唑烷酮助剂进行烯酰基部分进行的实验相比，这是一个改进。此外，与先前的工作相比，对映选择性也得到了改善，并且获得了高达73％的ee，这是这些金属催化的exo-selected
• Control of Diastereo- and Enantioselectivity in Metal-Catalyzed 1,3-Dipolar Cycloaddition Reactions of Nitrones with Alkenes. Experimental and Theoretical Investigations
  作者：Kurt V. Gothelf、Rita G. Hazell、Karl Anker Jørgensen

  DOI：10.1021/jo951204e

  日期：1996.1.1

  The scopes and limitations of the catalytic effects of achiral and chiral Mg(II) and Cu(II) complexes on the stereochemistry of the 1,3-dipolar cycloaddition reaction of nitrones with alkenes have been investigated. A remarkably high degree of endo-selectivity (endo/exo > 20) is induced in the 1,3-dipolar cycloaddition reaction by the presence of a catalytic amount of, especially, a Mg(II)-phenanthroline complex. The diastereochemical assignment of the product is confirmed by an X-ray crystallographic determination of the structure of the exo-isoxazolidine. By the reaction of an alkene bearing a chiral auxiliary, with different nitrones and a catalytic amount of the Mg(II)-phenanthroline complex, one of four possible diastereomers of the isoxazolidines is exclusively formed. The absolute stereochemistry of this product is also assigned by an X-ray crystallographic investigation. The presence of a catalytic amount of a chiral Mg(II)-bisoxazoline complex in the 1,3-dipolar cycloaddition reaction leads to high endo-selectivity and occasionally with an ee > 80%. The reaction mechanism of the Mg(II)-catalyzed reaction is discussed on the basis of the experimental results and semiempirical quantum chemical calculations. The calculations are used to account for the catalytic effect of the Mg(II)-ligand complexes and to determine transition state energies for both the uncatalyzed and Mg(II)-ligand-catalyzed reactions.