(2R,3R,5S,6S)-2,3-diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl<1,4>dioxane | 173371-54-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,5S,6S)-2,3-diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl<1,4>dioxane
• 英文别名: [(2S,3S,5R,6R)-5,6-diethoxy-3-(hydroxymethyl)-5,6-dimethyl-1,4-dioxan-2-yl]methanol
• CAS: 173371-54-5
• 化学式: C₁₂H₂₄O₆
• 分子量: 264.319
• InChiKey: PCHSKUZDCJPVLS-NNYUYHANSA-N

物化性质

• 沸点：
  365.8±42.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3R,5S,6S)-2,3-diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl<1,4>dioxane 在 4-二甲氨基吡啶 作用下， 以 吡啶 、 二氯甲烷 、 甲苯 为溶剂， 反应 60.0h， 生成 (1S,5S,6R,7R,8S,12S,14R,15R)-14,15-Diethoxy-14,15-dimethyl-6,7-diphenyl-3,10,13,16-tetraoxa-tricyclo[10.4.0.0^5,8]hexadecane-4,9-dione
  参考文献：
  名称：

  Investigations of the Asymmetric Intramolecular [2 + 2] Photocycloaddition and Its Application as a Simple Access to Novel C₂-Symmetric Chelating Bisphosphanes Bearing a Cyclobutane Backbone

  摘要：

  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.

  DOI：

  10.1021/jo960556y
• 作为产物：
  描述：

  3,3-二乙氧基-2-丁酮 在 lithium aluminium tetrahydride 、 氢气 作用下， 生成 (2R,3R,5S,6S)-2,3-diethoxy-5,6-bis(hydroxymethyl)-2,3-dimethyl<1,4>dioxane
  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

• 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。
• Synthesis and diastereoselective Diels–Alder reactions of homochiral C2-symmetric butane-1,2-diacetal-based 1,3-dienes
  作者：Bruno Linclau、Philip J. Clarke、Mark E. Light

  DOI：10.1016/j.tetlet.2009.10.015

  日期：2009.12

  The C2-symmetric, butane diacetal (BDA) auxiliary-based dienes 2 and 3 are described, which display moderate to excellent diastereoselectivities in Diels–Alder reactions with a range of dienophiles under thermal and Lewis acid-catalysed conditions.

  描述了基于C 2对称的丁烷二缩醛（BDA）辅助基二烯2和3，它们在热和Lewis酸催化条件下，在Diels-Alder反应中，与多种亲二烯体反应，显示出中等至极好的非对映选择性。
• 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.
• US6576772B1
  申请人：——

  公开号：US6576772B1

  公开（公告）日：2003-06-10
• 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.