(2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester | 173371-52-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester
• 英文别名: (2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2,3-dicarboxylic acid diethyl ester；diethyl (2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2,3-dicarboxylate
• CAS: 173371-52-3
• 化学式: C₁₄H₂₄O₈
• 分子量: 320.34
• InChiKey: SAWKPTABYCCEQT-DMTCVQMQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以51.4%的产率得到(2R,3R,5S,6S)-5,6-双(羟甲基)-2,3-二甲氧基-2,3-二甲基-1,4-二氧己环
  参考文献：
  名称：

  Transacetalization of Diethyl Tartrate with Acetals of .alpha.-Dicarbonyl Compounds: A Simple Access to a New Class of C2-Symmetric Auxiliaries and Ligands

  摘要：

  A simple access to a new class of C-2-symmetric auxiliaries and ligands is based on the transacetalization of diethyl tartrate (1) with monoacetals of butane-2,3-dione in the key step. Acid-catalyzed reaction of 1 with 2 equiv of 3,3-diethoxybutan-2-one (2) gives the C-2-symmetric 1,4-dioxane 7 in 88% yield. Reduction of 7 with LiAlH4 affords the crystalline diol 9. The structure of 7 was established from the X-ray structure of 9. Dioxane 7 was converted by standard methodology into the diphosphine 24 and the TARTROL 22. Reaction of 1 with 3,3-dimethoxybutan-2-one (3) in the presence of BF3-etherate gives in analogy to the formation of 7 the 1,4-dioxane 8. This compound was transformed into the diphosphine 25 and the TARTROL 23. The trans-diaxial relationship of the methoxy groups present in 8 could be deduced without X-ray analysis from the H-1-NMR spectrum of 23.

  DOI：

  10.1021/jo00130a019
• 作为产物：
  描述：

  L-(+)-酒石酸二乙酯 、 3,3-二甲氧基-2-丁酮 在 三氟化硼乙醚 作用下， 以 乙酸乙酯 为溶剂， 反应 6.0h， 以63.1%的产率得到(2R,3R,5R,6R)-5,6-dimethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Transacetalization of Diethyl Tartrate with Acetals of .alpha.-Dicarbonyl Compounds: A Simple Access to a New Class of C2-Symmetric Auxiliaries and Ligands

  摘要：

  A simple access to a new class of C-2-symmetric auxiliaries and ligands is based on the transacetalization of diethyl tartrate (1) with monoacetals of butane-2,3-dione in the key step. Acid-catalyzed reaction of 1 with 2 equiv of 3,3-diethoxybutan-2-one (2) gives the C-2-symmetric 1,4-dioxane 7 in 88% yield. Reduction of 7 with LiAlH4 affords the crystalline diol 9. The structure of 7 was established from the X-ray structure of 9. Dioxane 7 was converted by standard methodology into the diphosphine 24 and the TARTROL 22. Reaction of 1 with 3,3-dimethoxybutan-2-one (3) in the presence of BF3-etherate gives in analogy to the formation of 7 the 1,4-dioxane 8. This compound was transformed into the diphosphine 25 and the TARTROL 23. The trans-diaxial relationship of the methoxy groups present in 8 could be deduced without X-ray analysis from the H-1-NMR spectrum of 23.

  DOI：

  10.1021/jo00130a019

文献信息

• Enantiomerically Pure Bis-β-diketones: Valuable Building Blocks for Metallosupramolecular Chemistry
  作者：Markus Albrecht、Sabrina Dehn、Sören Schmid、Marita DeGroot

  DOI：10.1055/s-2006-950308

  日期：2007.1

  A series of enantiomerically pure bis-β-diketone derivatives was prepared by a Claisen-type condensation between protected tartaric acid diesters and several ketones. Hereby the tartaric acid unit is introduced as either a 2,2-dimethyldioxolane or as a 5,6-dimethoxy-5,6-dimethyl-1,4-dioxane derivative. The yields of the Claisen reaction are relatively low, but the starting materials are readily available, so that the one-step procedure leads to the bis-β-diketone derivatives in up to gram quantities.

  通过受保护的酒石酸二酯与几种酮的克莱森式缩合反应，制备出了一系列对映体纯度极高的双δ-二酮衍生物。酒石酸单元以 2,2-二甲基二氧戊环或 5,6-二甲氧基-5,6-二甲基-1,4-二氧戊环衍生物的形式引入。克莱森反应的收率相对较低，但起始原料很容易获得，因此一步法生产出的双δ-二酮衍生物的数量可达克。
• Homodinuclear f-f and Heterodinuclear f-p Lanthanide Helicates
  作者：Markus Albrecht

  DOI：10.1002/zaac.201000173

  日期：2010.9

  based on β-diketonate, catechol-acyl hydrazone and 2-amido-8-hydroxyquinoline ligands. Strongly emitting homodinuclear europium(III) complexes are obtained in addition to heterodinuclear coordination compounds. Some of the latter exhibit intramolecular energy transfer behaviour with internal quenching of an aluminium trisquinolinate and enhancement of the NIR emission at an ytterbium(III), neodymium(III)

  镧系元素螺旋由于它们能够在可见光或 NIR 区域发射而受到关注。在这种情况下，重要的是制备异双核螺旋并将它们用于研究不同复杂单元之间的分子内通讯过程。在这里，我们描述了基于 β-二酮酸酯、儿茶酚-酰基腙和 2-酰胺-8-羟基喹啉配体的同和异双核螺旋体的配体合成和自组装。除了异双核配位化合物外，还获得了强发射同双核铕 (III) 配合物。后者中的一些表现出分子内能量转移行为，三喹啉铝的内部淬灭和镱 (III)、钕 (III) 或铒 (III) 复合单元的 NIR 发射增强。
• Transacetalization of Diethyl Tartrate with Acetals of .alpha.-Dicarbonyl Compounds: A Simple Access to a New Class of C2-Symmetric Auxiliaries and Ligands
  作者：Ulrich Berens、Dieter Leckel、Susanne C. Oepen

  DOI：10.1021/jo00130a019

  日期：1995.12

  A simple access to a new class of C-2-symmetric auxiliaries and ligands is based on the transacetalization of diethyl tartrate (1) with monoacetals of butane-2,3-dione in the key step. Acid-catalyzed reaction of 1 with 2 equiv of 3,3-diethoxybutan-2-one (2) gives the C-2-symmetric 1,4-dioxane 7 in 88% yield. Reduction of 7 with LiAlH4 affords the crystalline diol 9. The structure of 7 was established from the X-ray structure of 9. Dioxane 7 was converted by standard methodology into the diphosphine 24 and the TARTROL 22. Reaction of 1 with 3,3-dimethoxybutan-2-one (3) in the presence of BF3-etherate gives in analogy to the formation of 7 the 1,4-dioxane 8. This compound was transformed into the diphosphine 25 and the TARTROL 23. The trans-diaxial relationship of the methoxy groups present in 8 could be deduced without X-ray analysis from the H-1-NMR spectrum of 23.