(2R,3R,7S)-2,3,7-trimethyl-1,4-dioxaspiro[4.5]decane | 33283-38-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,7S)-2,3,7-trimethyl-1,4-dioxaspiro[4.5]decane
• CAS: 33283-38-4；93451-80-0；93451-81-1
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: YHRKVJXJVGAYGU-IVZWLZJFSA-N

物化性质

• 沸点：
  209.2±8.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-环己烯-1-酮 在 对甲苯磺酸 2S-methyloxymethylpyrrolidine 、 copper(I) thiocyanate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 (2R,3R,7S)-2,3,7-trimethyl-1,4-dioxaspiro[4.5]decane
  参考文献：
  名称：

  Asymmetric induction in the conjugate addition reactions of chiral organo(hetero)cuprates

  摘要：

  DOI：

  10.1021/ja00241a021

文献信息

• Clathrates of TETROL: Further Aspects of the Selective Inclusion of Methylcyclohexanones in Their Energetically Unfavorable Axial Methyl Conformations
  作者：Benita Barton、Mino R. Caira、Eric C. Hosten、Cedric W. McCleland、Selwyn Weitz

  DOI：10.1021/acs.joc.5b01067

  日期：2015.7.17

  (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) functions as a highly efficient host for the inclusion of cyclohexanone and 2-, 3-, and 4-methylcydohexanone, all with 1:1 host/guest ratios. Most extraordinarily, the 3- and 4-methyl isomers are uniquely included in their higher energy axial methyl conformations rather than as their more energetically favorable equatorial analogues. In contrast, 2-methylcyclohexanone is included more conventionally in the equatorial methyl conformation. During recrystallization of TETROL from racemic 2- and 3-methylcyclohexanone, some preference is shown by the host for the (R)-enantiomer. In the latter case, this is attributed to a much stronger H-bond between a hydroxyl group of TETROL and the carbonyl group of the (R)-enantiomer (O center dot center dot center dot O 2.621(2) angstrom) compared with a significantly weaker H-bond to the (S)-enantiomer (3.125(8) angstrom). In the former instance, hydrogen-bond strengths to both enantiomers are similar, but the (R)-enantiomer engages in three (guest)CH center dot center dot center dot pi(host) and three (guest)H center dot center dot center dot C-ar(host) contacts, whereas fewer interactions of these types are observed for the (S)-enantiomer. Calculations of geometries of the guest cyclohexanones were determined at the MP2/6-311++G(2df,2p) level and compared with those obtained at the G3(MP2) level. Finally, an interesting correlation between crystal packing indices for the three methylcyclohexanone clathrates and their respective desolvation onset temperatures was identified.

  (+)−(2R,3R)−1,1,4,4−四苯基丁烷−1,2,3,4−四醇（TETROL）作为宿主，能高效地与环己酮以及2−、3−和4−甲基环己酮形成包结物，所有包结物的主客体比值均为1:1。特别值得注意的是，3−和4−甲基异构体的独特之处在于它们以能量较高的轴向甲基构象被包结，而非更能量有利的赤道类似物。相比之下，2−甲基环己酮则更常规地以赤道甲基构象被包结。在从外消旋2−和3−甲基环己酮重结晶TETROL时，宿主倾向于结合(R)-对映体。在后一种情况下，这归因于TETROL的一个羟基与(R)-对映体的羰基之间形成了比与(S)-对映体之间强得多的氢键（O···O 距离分别为2.621(2) 埃和3.125(8) 埃）。在前一种情况下，与两种对映体的氢键强度相似，但(R)-对映体形成了三个（客体）CH···π（主体）和三个（客体）H···C-arah（主体）接触，而(S)-对映体则表现出较少的此类相互作用。客体环己酮的几何结构在MP2/6-311++G(2df,2p) 水平上进行了计算，并与G3(MP2) 水平下的结果进行了比较。最后，发现三种甲基环己酮固态水合物的晶体堆积指数与其各自的脱溶剂起始温度之间存在有趣的相关性。
• Synthesis of β-Alkyl Cyclopentanones in High Enantiomeric Excess via Copper-Catalyzed Asymmetric Conjugate Reduction
  作者：Yasunori Moritani、Daniel H. Appella、Valdas Jurkauskas、Stephen L. Buchwald

  DOI：10.1021/ja0009525

  日期：2000.7.1
• Asymmetric induction in the conjugate addition reactions of chiral organo(hetero)cuprates
  作者：R. Karl Dieter、Maritherese Tokles

  DOI：10.1021/ja00241a021

  日期：1987.4