(2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester | 173371-53-4

• 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-diethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester
• 英文别名: diethyl (2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl-1,4-dioxane-2,3-dicarboxylate
• CAS: 173371-53-4
• 化学式: C₁₆H₂₈O₈
• 分子量: 348.394
• InChiKey: VODQVTBJRXEBRJ-CZPYZCIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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-diethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (2R,3R,5S,6S)-2,3-diethoxy-2,3-dimethyl-5,6-bis(((methanesulfonyl)oxy)methyl)[1,4]dioxane
  参考文献：
  名称：

  手性C（2）对称配体与酒石酸酯衍生的1，4-二恶烷骨架：合成和不对称氢化中的应用。

  摘要：

  手性1,4-二苯基膦5-7以及硫醚8是由酒石酸盐合成的，采用Ley的“ BDA”和“ Dispoke”方法作为关键步骤。含5-7的铑（I）配合物是有效的催化剂，可用于β-取代的酰胺和MOM保护的β-羟基酰胺的不对称加氢，从而提供了94-> 99％ee的手性胺或β-氨基醇。这些结果表明，具有一般结构2的配体中的1，4-二恶烷骨架在稳定金属-配体螯合物构象中起重要作用。与具有一般结构1的类似配体相比，配体2具有更高的对映选择性。

  DOI：

  10.1021/jo020250t
• 作为产物：
  描述：

  L-(+)-酒石酸二乙酯 、 3,3-二乙氧基-2-丁酮 在 氢气 作用下， 以88%的产率得到(2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  (2R,3R,5S,6S)-2,3-Diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl-1,4-dioxane

  摘要：

  The title compound, C12H24O6, was synthesized and subjected to an X-ray structure determination. The aim of this structure analysis was to determine the relative orientation of two vicinal ethoxy groups in its precursor, diethyl (2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl-1,4-dioxane-2, 3-dicarboxylate, from which the title compound can be generated by a reaction that retains the absolute configuration of the molecular skeleton.

  DOI：

  10.1107/s0108270195012194

文献信息

• 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.
• Investigations of the Asymmetric Intramolecular [2 + 2] Photocycloaddition and Its Application as a Simple Access to Novel <i>C</i>₂-Symmetric Chelating Bisphosphanes Bearing a Cyclobutane Backbone
  作者：Dieter Haag、Hans-Dieter Scharf

  DOI：10.1021/jo960556y

  日期：1996.1.1

  The asymmetric intramolecular [2 + 2] photocycloaddition of alpha,beta-enoates was evaluated as a simple access to the novel Ct-symmetric bisphosphanes 22 and 27 possessing a cyclobutane backbone. A source of different chiral auxiliaries for investigations of the photochemical key step was provided by the transacetalization of dialkyl tartrates 3 with the corresponding 3,3-dialkoxybutan-2-ones 4. An insight into the selection mechanism was gained by temperature dependent measurements on the irradiation of the dicinnamates 10a-d, since the corresponding Eyring diagram discloses strictly linear functions as well as an isoselective relationship. Diol 8a turned out to be a structurally optimized auxiliary in terms of chiral induction and product crystallization and was also successfully applied in the first asymmetric photodimerization of 2-indenecarboxylic acid esters. Indeed, in this case excellent diastereoselectivities were achieved, too, but head-to-tail dimers 16a and 16b were formed predominantly. Diesters 11a and 16a were converted by standard procedures into the desired enantiopure 1,4-diphosphane 22 and 1,5-diphosphane 27. Furthermore, the hitherto unknown absolute configuration of delta-truxinic acid was elucidated from a single crystal X-ray structure analysis of 11a.
• Chiral <i>C</i>₂-Symmetric Ligands with 1,4-Dioxane Backbone Derived from Tartrates:  Syntheses and Applications in Asymmetric Hydrogenation
  作者：Wenge Li、Jason P. Waldkirch、Xumu Zhang

  DOI：10.1021/jo020250t

  日期：2002.11.1

  Chiral 1,4-diphenylphosphines 5-7 as well as thioether 8 were synthesized from tartrates employing Ley's "BDA" and "Dispoke" methodologies as the key step. Rhodium(I) complexes with 5-7 are efficient catalysts for the asymmetric hydrogenation of beta-substituted enamides and MOM-protected beta-hydroxyl enamides, which furnished chiral amines or beta-amino alcohols with 94-->99% ee. These results indicated

  手性1,4-二苯基膦5-7以及硫醚8是由酒石酸盐合成的，采用Ley的“ BDA”和“ Dispoke”方法作为关键步骤。含5-7的铑（I）配合物是有效的催化剂，可用于β-取代的酰胺和MOM保护的β-羟基酰胺的不对称加氢，从而提供了94-> 99％ee的手性胺或β-氨基醇。这些结果表明，具有一般结构2的配体中的1，4-二恶烷骨架在稳定金属-配体螯合物构象中起重要作用。与具有一般结构1的类似配体相比，配体2具有更高的对映选择性。
• (2R,3R,5S,6S)-2,3-Diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl-1,4-dioxane
  作者：U. Berens、G. Raabe

  DOI：10.1107/s0108270195012194

  日期：1996.3.15

  The title compound, C12H24O6, was synthesized and subjected to an X-ray structure determination. The aim of this structure analysis was to determine the relative orientation of two vicinal ethoxy groups in its precursor, diethyl (2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl-1,4-dioxane-2, 3-dicarboxylate, from which the title compound can be generated by a reaction that retains the absolute configuration of the molecular skeleton.