diethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate | 134745-01-0

• 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-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate
• 英文别名: diethyl (4R,5R)-2-methoxy-2-methyl-1,3-dioxolane-4,5-dicarboxylate
• CAS: 134745-01-0
• 化学式: C₁₁H₁₈O₇
• 分子量: 262.26
• InChiKey: BTWRRLKRALIAAU-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  diethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate 在 四氯化钛 、 二异丁基氢化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (4R,5R)-2-(2-Hydroxy-cyclohexyl)-2-methyl-[1,3]dioxolane-4,5-dicarboxylic acid diethyl ester
  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-(+)-酒石酸二乙酯 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到diethyl (4R)-trans-2-methoxy-2-methyl-1,3-dioxolan-4,5-dicarboxylate
  参考文献：
  名称：

  (-)-Posticlure 的有效合成：Orgyia postica 的性信息素

  摘要：

  描述了从 L-酒石酸二乙酯中高效合成 (-)-posticlure，这是在 Orgyia postica 中发现的第一种反式环氧化物性信息素。合成分七个步骤完成，总产率为 27%。该合成策略以双维蒂希烯化和二醇立体选择性一锅法转化为环氧化物为关键步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200700449

文献信息

• Enantioselective acylation of enolates; the reaction of (4R)-trans-diethyl 2-alkyl-2-methoxy-1,3-dioxolane-4,5-dicarboxylates with E- and Z-silyl enol ethers
  作者：Tiziana Basile、Luigi Longobardo、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1039/c39910000391

  日期：——

  The stereoselectivity of the Lewis acid induced acylation of open-chain silyl enoi ethers by chiral orthoesters is strongly affected by the CC bond configuration: both Z and E silyl enol ethers are acylated in good isolated yields, but the Z isomers give rise to a 1 : 1 ratio of diastereoisomeric monoprotected 1,3-diketones, while excellent stereoselectivities are obtained with E enols.

  路易斯酸诱导的开链硅醇醚与手性邻醇酸酯的酰化反应的立体选择性受到碳碳键构型的强烈影响：Z型和E型硅醇醚均可获得良好的单体收率，但Z型异构体产生1:1的立体异构单保护1,3-二酮的比例，而E型醇则获得出色的立体选择性。
• 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.
• An Efficient Synthesis of (–)-Posticlure: The Sex Pheromone ofOrgyia postica
  作者：Rodney A. Fernandes

  DOI：10.1002/ejoc.200700449

  日期：2007.10

  An efficient multigram synthesis of (–)-posticlure, the first trans-epoxide sex pheromone found in Orgyia postica, from diethyl L-tartrate is described. The synthesis was completed in seven steps and 27 % overall yield. The synthetic strategy features double-Wittig olefination and a stereoselective one-pot conversion of diol to epoxide as the key steps. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  描述了从 L-酒石酸二乙酯中高效合成 (-)-posticlure，这是在 Orgyia postica 中发现的第一种反式环氧化物性信息素。合成分七个步骤完成，总产率为 27%。该合成策略以双维蒂希烯化和二醇立体选择性一锅法转化为环氧化物为关键步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)