dimethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate | 139015-86-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dimethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate
• 英文别名: (4R,5R)-4,5-bis(methoxycarbonyl)-2-methyl-2-methoxy-1,3-dioxolane；dimethyl (4R,5R)-2-methoxy-2-methyl-1,3-dioxolane-4,5-dicarboxylate
• CAS: 139015-86-4
• 化学式: C₉H₁₄O₇
• 分子量: 234.206
• InChiKey: PTIYHBDGGNYAMR-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-环己烯氧基三甲基硅烷 、 dimethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以80%的产率得到dimethyl (4R)-trans-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolan-4,5-dicarboxylate
  参考文献：
  名称：

  Chiral orthoesters in organic synthesis: Novel reagents for the enantioselective acylation of silylenolethers

  摘要：

  Dialkyl trans-2-alkoxy-2-alkyl-1,3-dioxolan-4,5-dicarboxylates and the corresponding N,N,N,N-tetramethyl-4,5-diamides have been prepared respectively from dialkyl tartrates or tartaric acid diamides. They smoothly reacted with silylenolethers in the presence of Lewis acids to give enantiomerically enriched (up to 90% d.e.) monoprotected 1,3-diketones. A dramatic dependence of the stereochemical outcome from the configuration of the enolic double bond of 4 has been observed. The products can be stereoselectively reduced to give configurationally defined monoprotected 3-ketols.

  DOI：

  10.1016/s0040-4020(01)90792-6
• 作为产物：
  描述：

  原乙酸三甲酯 、 L-(+)-酒石酸二甲酯 在 硫酸 作用下， 以 苯 为溶剂， 以98%的产率得到dimethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate
  参考文献：
  名称：

  Chiral orthoesters in organic synthesis: Novel reagents for the enantioselective acylation of silylenolethers

  摘要：

  Dialkyl trans-2-alkoxy-2-alkyl-1,3-dioxolan-4,5-dicarboxylates and the corresponding N,N,N,N-tetramethyl-4,5-diamides have been prepared respectively from dialkyl tartrates or tartaric acid diamides. They smoothly reacted with silylenolethers in the presence of Lewis acids to give enantiomerically enriched (up to 90% d.e.) monoprotected 1,3-diketones. A dramatic dependence of the stereochemical outcome from the configuration of the enolic double bond of 4 has been observed. The products can be stereoselectively reduced to give configurationally defined monoprotected 3-ketols.

  DOI：

  10.1016/s0040-4020(01)90792-6

文献信息

• Solid-state and solution conformational analysis of tartrate-derived 1,3-dioxolanes and 1,3,2-dioxaborolanes
  作者：William R. Roush、Andrew M. Ratz、Jill A. Jablonowski

  DOI：10.1021/jo00033a027

  日期：1992.3

  Solid-state (X-ray) and solution conformational analyses of tartrate ester derived 1,3-dioxolanes and 1,3,2-dioxaborolanes are described. The solid-state conformation of dimethyl benzylidenetartrate (5) was found to be one in which the two carbomethoxy groups are pseudoaxial and the ester carbonyls eclipse the adjacent dioxolane C-O bonds. This parallels exactly the conformation previously proposed for the 1,3,2-dioxaborolane unit in the transition state of the reactions of tartrate ester modified allylboronates 1-3 and aldehydes. A correlation was developed between the solution and solid-state conformations of 1,3-dioxolanes 5-7 based on the observed J4,5 coupling constants and the H-4-C-C-H-5 dihedral angle obtained from the X-ray crystal structures. A high resolution variable-temperature H-1 NMR study of 1,3-dioxolane 5 in THF-d8 revealed that J4,5 decreased from 3.72 Hz at 23-degrees-C to 2.91 Hz at -80-degrees-C, providing evidence that the diaxial conformation is increasingly favored as the temperature is decreased. A high resolution variable-temperature H-1 NMR study of ortho ester 12, prepared from dimethyl tartrate and trimethyl orthoacetate, in THF-d8 similarly revealed J4,5 = 5.25 Hz at 23-degrees-C and J4,5 = 4.60 Hz at -80-degrees-C. An analogous solution conformation analysis was also performed with 1,3,2-dioxaborolane derivatives 16 and 17 prepared from methyl trifluoroethyl tartrate (15). Variable-temperature H-1 NMR analysis of 17 in toluene-d8 revealed that J4,5 decreased to a value of J4,5 = 5.0 Hz at 23-degrees-C to J4,5 = 4.3 Hz at -60-degrees-C. The significance of these data to the mechanism of asymmetric induction in the reactions of the tartrate ester modified allylboronates 1-3 and aldehydes is discussed.
• Chiral orthoesters in organic synthesis: Novel reagents for the enantioselective acylation of silylenolethers
  作者：Luigi Longobardo、Giovanna Mobbili、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1016/s0040-4020(01)90792-6

  日期：1992.1

  Dialkyl trans-2-alkoxy-2-alkyl-1,3-dioxolan-4,5-dicarboxylates and the corresponding N,N,N,N-tetramethyl-4,5-diamides have been prepared respectively from dialkyl tartrates or tartaric acid diamides. They smoothly reacted with silylenolethers in the presence of Lewis acids to give enantiomerically enriched (up to 90% d.e.) monoprotected 1,3-diketones. A dramatic dependence of the stereochemical outcome from the configuration of the enolic double bond of 4 has been observed. The products can be stereoselectively reduced to give configurationally defined monoprotected 3-ketols.