(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 | 173371-55-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (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
• 英文名称: (2S,3S,5R,6R)-2,3-bis(hydroxymethyl)-5,6-dimethoxy-5,6-dimethyl<1,4>dioxane
• 英文别名: (2S,3S,5R,6R)-5,6-dimethoxy-5,6-dimethyl-2,3-di(hydroxymethyl)-[1,4]-dioxane；(2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis(hydroxymethyl)[1,4]dioxane；(2S,3S,5R,6R)-2,3-bis(hydroxymethyl)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane；(2S,3S,5R,6R)-2,3-bis(hydroxymethyl)-5,6-dimethyl-5,6-dimethoxy-1,4-dioxane；(3-hydroxymethyl-5,6-dimethoxy-5,6-dimethyl[1,4]dioxan-2-yl)methylalcohol；(2R,3R,5S,6S)-5,6-Bis(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane；[(2S,3S,5R,6R)-3-(hydroxymethyl)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxan-2-yl]methanol
• CAS: 173371-55-6
• 化学式: C₁₀H₂₀O₆
• 分子量: 236.265
• InChiKey: RAIJJZVROJTPEU-AXTSPUMRSA-N

物化性质

• 熔点：
  119.0 to 123.0 °C

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  16
• 可旋转键数：
  4
• 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)-5,6-双(羟甲基)-2,3-二甲氧基-2,3-二甲基-1,4-二氧己环 在 palladium on activated charcoal 吡啶 、 四氯化碳 、 sodium azide 、 氢气 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 80.0 ℃ 、34.47 kPa 条件下， 反应 117.5h， 生成 (2S,3S,5R,6R)-5,6-dimethoxy-5,6-dimethyl-3-[(p-toluenesulfonylamino)-methyl]-[1,4]-dioxan-2-ylmethyl p-toluenesulfonate
  参考文献：
  名称：

  Teresa Barros; Phillips, Ana Maria Faisca, Molecules, 2006, vol. 11, # 2-3, p. 177 - 196

  摘要：

  DOI：
• 作为产物：
  描述：

  3,3-二甲氧基-2-丁酮 在 lithium aluminium tetrahydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 70.0 ℃ 、9.33 kPa 条件下， 反应 7.0h， 生成 (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：

  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

文献信息

• Synthesis of<i>C</i>₂-Symmetric Bisphosphine Ligands from Tartaric Acid, and Their Performance in the Pd-Catalyzed Asymmetric<i>O</i>-Allylation of a Phenol
  作者：Mehmet Dindaroğlu、Sema Akyol Dinçer、Hans-Günther Schmalz

  DOI：10.1002/ejoc.201402326

  日期：2014.7

  Starting from tartaric acid derived chiral diols or dicarboxylic acid dichlorides with either a 2,2-dimethyl-1,3-dioxolane (Taddol) or a 2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (Tatrol) core structure, and BH3-protected ortho-phosphanyl phenols, a set of fourteen new C2-symmetric diphosphine ligands was synthesized. In addition, three related ligands were obtained from ortho-diphenylphosphino-anilines

  从酒石酸衍生的手性二醇或二羧酸二氯化物与 2,2-二甲基-1,3-二氧戊环 (Taddol) 或 2,3-二甲氧基-2,3-二甲基-1,4-二氧六环 (Tatrol) 开始核心结构和 BH3 保护的邻膦酰基苯酚，合成了一组 14 个新的 C2 对称二膦配体。此外，三个相关的配体是从邻二苯基膦基苯胺中获得的。然后使用巴豆基甲基碳酸酯作为试剂在 Pd 催化的 4-甲氧基苯酚的对映选择性 O-烯丙基化反应中测试完全表征的配体。此外，还研究了使用碳酸巴豆基 4-甲氧基苯基酯作为底物的拟分子内反应变体。所谓的 Trost 配体被用作参考。尽管 Trost 配体 (3 mol-%) 的 ee 含量高达 84%，
• 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。
• New organocatalysts derived from tartaric and glyceric acids for direct aldol reactions
  作者：Christopher D. Maycock、M. Rita Ventura

  DOI：10.1016/j.tetasy.2012.08.008

  日期：2012.9

  of several new pyrrolidine based asymmetric organocatalysts derived from tartaric, glyceric acids and a pyrrolidine moiety is described with a study of their application in the development of an enantioselective aldol protocol. The influence of different proton donor groups, such as a primary hydroxyl or a carboxylic acid group, or their absence, on the efficiency of the organocatalyst was studied

  描述了几种新的由酒石酸，甘油酸和吡咯烷部分衍生的基于吡咯烷的不对称有机催化剂的合成，并研究了它们在对映选择性羟醛方案的开发中的应用。研究了不同的质子供体基团，例如伯羟基或羧酸基团，或它们的不存在对有机催化剂效率的影响。发现酒石酸衍生的催化剂的构型和刚性的2,3-二缩丁烷的存在对醛醇缩合反应的立体选择性结果有很大的影响。
• Stereoselectivity in Metal Carbene Addition to a Carbon-Carbon Triple Bond Tied to the Reactant Diazoacetate Through a Chiral Linker
  作者：Michael P. Doyle、Thomas M. Weathers、Yuanhua Wang

  DOI：10.1002/adsc.200600349

  日期：2006.11

  of a carbon-carbon triple bond onto a metal carbene for cyclopropene formation is opposite to that of a carbon-carbon double bond in the same system. Diazoacetates prepared from the butane-2,3-diacetals (BDA) of (L)- and (D)-threitol were employed to examine diastereoselectivity in cyclopropenation. The absolute configuration of the predominant isomer was opposite in intramolecular metal carbene additions

  在同一系统中，碳-碳三键在金属碳烯上形成环丙烯的轨迹与碳-碳双键的轨迹相反。由（L）-和（D）-苏糖醇的丁烷-2,3-二缩醛（BDA）制得的重氮乙酸酯用于检验环丙烷化中的非对映选择性。在向炔丙基和烯丙基取代基的分子内金属卡宾中，主要异构体的绝对构型是相反的。氨基甲酸二（II）氨基甲酸酯催化的重氮分解反应中的非对映选择性高达99：1，对底物和催化剂的匹配/不匹配选择性取决于催化剂的构型，并且优先顺序为：Rh 2（MEPY）4 > Rh 2（MEOX）4 > Rh2（MEAZ）4 > Rh 2（MPPIM）4。Cu（CH 3 CN）4 PF 6 / PhBox系统催化的反应以互补的匹配/不匹配选择性产生相同的非对映异构体，该选择性也达到99：1。