cis-1,2-Cyclohexanedimethyl bis(2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate) | 235779-96-1

• 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: cis-1,2-Cyclohexanedimethyl bis(2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate)
• 英文别名: [(1R,2S)-2-[(2,2,4,4-tetramethyl-1,3-oxazolidine-3-carbonyl)oxymethyl]cyclohexyl]methyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 235779-96-1
• 化学式: C₂₄H₄₂N₂O₆
• 分子量: 454.607
• InChiKey: RRNLCHMSIIFVTL-HDICACEKSA-N

物化性质

• 沸点：
  514.887±50.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.060±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  77.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  cis-1,2-Cyclohexanedimethyl bis(2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate) 在 甲烷磺酸 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以89%的产率得到cis-1,2-Cyclohexanedimethyl bis[N-(2-hydroxy-1,1-dimethylethyl)carbamate]
  参考文献：
  名称：

  Efficient Desymmetrization ofmeso-cis-1,2-Cyclohexanedimethanol with Differentiation between Diastereotopic and Enantiotopic C−H Bonds by (−)-Sparteine-Mediated Deprotonation

  摘要：

  The deprotonation of a dicarbamate prepared from cis-1,2-cyclohexanedimethanol by sec-butyllithium/(-)-sparteine proceeds with efficient selection between the enantiotopic branches and their diastereotopic protons with high preference for the pro-S proton at the R branch to afford the intermediate, configurationally stable lithium compound as a single diastereomer. Trapping of this intermediate by electrophiles (DOMe, CO2, CH3I, Me3SiCl, or R3SnCl) takes place with retention of the configuration to yield highly enantiomerically and diastereomerically enriched substitution products, which are easily converted to diols, to anellated tetrahydrofurans, or to gamma-lactones. The chiral base is also capable of efficient kinetic resolution of the racemic alpha-deuterated starting material, by the utilization of an extraordinarily high kinetic H/D isotope effect within the deprotonation step. The, presumably first example of the kinetic resolution of a racemic stannane by lithiodestannylation, utilizing methyllithium/(-)-sparteine, is reported.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1905::aid-chem1905>3.0.co;2-4
• 作为产物：
  描述：

  cis-1,2-Cyclohexanedimethyl bis[N-(2-hydroxy-1,1-dimethylethyl)carbamate] 在 甲醇 、 sodium hydride 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 19.5h， 生成 cis-1,2-Cyclohexanedimethyl bis(2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate)
  参考文献：
  名称：

  Efficient Desymmetrization ofmeso-cis-1,2-Cyclohexanedimethanol with Differentiation between Diastereotopic and Enantiotopic C−H Bonds by (−)-Sparteine-Mediated Deprotonation

  摘要：

  The deprotonation of a dicarbamate prepared from cis-1,2-cyclohexanedimethanol by sec-butyllithium/(-)-sparteine proceeds with efficient selection between the enantiotopic branches and their diastereotopic protons with high preference for the pro-S proton at the R branch to afford the intermediate, configurationally stable lithium compound as a single diastereomer. Trapping of this intermediate by electrophiles (DOMe, CO2, CH3I, Me3SiCl, or R3SnCl) takes place with retention of the configuration to yield highly enantiomerically and diastereomerically enriched substitution products, which are easily converted to diols, to anellated tetrahydrofurans, or to gamma-lactones. The chiral base is also capable of efficient kinetic resolution of the racemic alpha-deuterated starting material, by the utilization of an extraordinarily high kinetic H/D isotope effect within the deprotonation step. The, presumably first example of the kinetic resolution of a racemic stannane by lithiodestannylation, utilizing methyllithium/(-)-sparteine, is reported.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1905::aid-chem1905>3.0.co;2-4

文献信息

• Efficient Desymmetrization ofmeso-cis-1,2-Cyclohexanedimethanol with Differentiation between Diastereotopic and Enantiotopic C−H Bonds by (−)-Sparteine-Mediated Deprotonation
  作者：Jan van Bebber、Hartmut Ahrens、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1905::aid-chem1905>3.0.co;2-4

  日期：1999.6.4

  The deprotonation of a dicarbamate prepared from cis-1,2-cyclohexanedimethanol by sec-butyllithium/(-)-sparteine proceeds with efficient selection between the enantiotopic branches and their diastereotopic protons with high preference for the pro-S proton at the R branch to afford the intermediate, configurationally stable lithium compound as a single diastereomer. Trapping of this intermediate by electrophiles (DOMe, CO2, CH3I, Me3SiCl, or R3SnCl) takes place with retention of the configuration to yield highly enantiomerically and diastereomerically enriched substitution products, which are easily converted to diols, to anellated tetrahydrofurans, or to gamma-lactones. The chiral base is also capable of efficient kinetic resolution of the racemic alpha-deuterated starting material, by the utilization of an extraordinarily high kinetic H/D isotope effect within the deprotonation step. The, presumably first example of the kinetic resolution of a racemic stannane by lithiodestannylation, utilizing methyllithium/(-)-sparteine, is reported.