diethyl (4R)-trans-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolan-4,5-dicarboxylate | 140630-58-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: diethyl (4R)-trans-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolan-4,5-dicarboxylate
• 英文别名: diethyl (4R,5R)-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolane-4,5-dicarboxylate
• CAS: 140630-58-6
• 化学式: C₁₆H₂₄O₇
• 分子量: 328.362
• InChiKey: NQKVMGYVMQCDTC-SKVSWLLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  23.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  diethyl (4R)-trans-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolan-4,5-dicarboxylate 在 三氟化硼乙醚 、 二异丁基氢化铝 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 trans-1-(2-hydroxycyclohexyl)ethanone
  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：

  1-环己烯氧基三甲基硅烷 、 (4R,5R)-2-Ethoxy-2-methyl-[1,3]dioxolane-4,5-dicarboxylic acid diethyl ester 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以80%的产率得到diethyl (4R)-trans-2-methyl-2-(2-oxocyclohexyl)-1,3-dioxolan-4,5-dicarboxylate
  参考文献：
  名称：

  新型对映选择性酰化剂。手性原酸酯和甲硅烷基醚的反应，作为光学活性单保护的1，3-二羰基化合物的一种途径

  摘要：

  通过将甲硅烷基醚与衍生自二乙基或二异丙基（R，R）-酒石酸酯的手性原酸酯酰化，开发了一种新的对映选择性路线，用于单保护的2-取代-1,3-二羰基化合物。从环状烯醇硅烷开始，可以获得良好的产率和立体选择性。

  DOI：

  10.1039/c39900000759

文献信息

• BASILE, TIZIANA;LONGOBARDO, LUIGI;TAGLIAVINI, EMILIO;TROMBINI, CLAUDIO;UM+, J. CHEM. SOC. CHEM. COMMUN.,(1990) N0, C. 759-760
  作者：BASILE, TIZIANA、LONGOBARDO, LUIGI、TAGLIAVINI, EMILIO、TROMBINI, CLAUDIO、UM+

  DOI：——

  日期：——
• Novel enantioselective acylating agents. The reactions of chiral ortho esters and silylenol ethers as a route to optically active monoprotected 1,3-dicarbonyl compounds
  作者：Tiziana Basile、Luigi Longobardo、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1039/c39900000759

  日期：——

  A novel enantioselective route to monoprotected 2-substituted-1,3-dicarbonyl compounds has been developed via acylation of silylenol ethers with chiral ortho esters derived from diethyl or di-isopropyl (R,R)-tartrates; good yields and stereoselectivity can be achieved starting from cyclic enolsilanes.

  通过将甲硅烷基醚与衍生自二乙基或二异丙基（R，R）-酒石酸酯的手性原酸酯酰化，开发了一种新的对映选择性路线，用于单保护的2-取代-1,3-二羰基化合物。从环状烯醇硅烷开始，可以获得良好的产率和立体选择性。
• 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.