(2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis(((toluene-4-sulfonyl)oxy)methyl)<1,4>dioxane | 173371-57-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis(((toluene-4-sulfonyl)oxy)methyl)<1,4>dioxane
• 英文别名: (2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-di(toluene-4-sulfonyloxymethyl)-<1,4>dioxane；(2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis([(toluene-4-sulfonyl)oxy]methyl)[1,4]dioxane；[(2S,3S,5R,6R)-5,6-dimethoxy-5,6-dimethyl-3-[(4-methylphenyl)sulfonyloxymethyl]-1,4-dioxan-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 173371-57-8
• 化学式: C₂₄H₃₂O₁₀S₂
• 分子量: 544.644
• InChiKey: CIZLVXBAALAMNQ-CJRSTVEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis(((toluene-4-sulfonyl)oxy)methyl)<1,4>dioxane 在 三乙基硅烷 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 以61.7%的产率得到(2S,3S,5R,6R)-2,3-bis(toluene-4-sulfonyloxymethyl)-5,6-dimethyl-[1,4]dioxane
  参考文献：
  名称：

  New seven-membered ring chelates with unexpected enantioselectivity induction in asymmetric hydrogenation — hint for a constant relative enantioselectivity Q for pairs of substrates determined by the structure of the catalysts

  摘要：

  A series of new chiral 2,3-bis(diphenylphosphanylmethyl)-[1,4]dioxane-rhodium(I) chelates as catalysts in the asymmetric hydrogenation of (Z)-2-N-acylamino-acrylate derivatives, induce in the opposite direction compared with similar well-known catalysts possessing the same configuration, and lead to the unexpected product enantiomers. A thorough investigation of some substrate pairs led to the result that the relative enantioselectivity Q = q(H)/q(Me), the quotient of the enantiomeric ratios q for acid substrates (q(H)) and methyl esters (q(Me)), seems to be constant and characteristic for a catalyst with values influenced distinctly by the structure of the ligand. A new reduction of bisacetals to diethers by the reagent couple triethylsilane-tin tetrachloride was developed in order to obtain ligand 5a. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00248-0
• 作为产物：
  描述：

  3,3-二甲氧基-2-丁酮 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 吡啶 、 乙酸乙酯 为溶剂， 反应 8.5h， 生成 (2R,3R,5S,6S)-2,3-dimethoxy-2,3-dimethyl-5,6-bis(((toluene-4-sulfonyl)oxy)methyl)<1,4>dioxane
  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