(2,2-dimethylpropane-1,3-diyl)bis(naphthalen-2-ylsulfane) | 1296204-16-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2,2-dimethylpropane-1,3-diyl)bis(naphthalen-2-ylsulfane)
• 英文别名: 1,3-bis(2-naphthylthio)-2,2-dimethylpropane
• CAS: 1296204-16-4
• 化学式: C₂₅H₂₄S₂
• 分子量: 388.598
• InChiKey: VLLKBERSKPCXTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2,2-dimethylpropane-1,3-diyl)bis(naphthalen-2-ylsulfane) 在 bis(acetylacetonate)oxovanadium 、 (S)-2-(N-3',5'-diiodosalicylidene)-amino-3,3-dimethyl-1-butanol 、 双氧水 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以38%的产率得到2,2'-(2,2-dimethylpropane-1,3-diyldisulfinyl)dinaphthalene
  参考文献：
  名称：

  Synthesis of C3- and C2-symmetric tris- and bis-sulfoxide ligands by asymmetric oxidation

  摘要：

  A series of tris- and bis-sulfoxides were synthesized by multiple asymmetric oxidation of the corresponding sulfides. High enantioselectivities were obtained based on Horeau-type amplification of selectivity. Naphthyl-substituted sulfoxides allowed for higher selectivity and greater ease of purification. These sulfoxides were tested as ligands in rhodium-catalyzed olefin hydroacylation and 1,4-addition of phenyl boronic acid to 2-cyclohexen-1-one. While no enantioinduction was observed in hydroacylation, up to 80% ee was obtained for a tris-sulfoxide and a bis-sulfoxide ligand in the 1,4-addition. Bis-sulfoxides with flexible backbones gave lower and inversed enantioselectivity, suggesting backbone rigidity plays a key role in enantioinduction. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.02.023
• 作为产物：
  描述：

  2,2-二甲基-1,3-丙二醇 在 吡啶 、 sodium hydride 、 sodium iodide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 72.0h， 生成 (2,2-dimethylpropane-1,3-diyl)bis(naphthalen-2-ylsulfane)
  参考文献：
  名称：

  Synthesis of C3- and C2-symmetric tris- and bis-sulfoxide ligands by asymmetric oxidation

  摘要：

  A series of tris- and bis-sulfoxides were synthesized by multiple asymmetric oxidation of the corresponding sulfides. High enantioselectivities were obtained based on Horeau-type amplification of selectivity. Naphthyl-substituted sulfoxides allowed for higher selectivity and greater ease of purification. These sulfoxides were tested as ligands in rhodium-catalyzed olefin hydroacylation and 1,4-addition of phenyl boronic acid to 2-cyclohexen-1-one. While no enantioinduction was observed in hydroacylation, up to 80% ee was obtained for a tris-sulfoxide and a bis-sulfoxide ligand in the 1,4-addition. Bis-sulfoxides with flexible backbones gave lower and inversed enantioselectivity, suggesting backbone rigidity plays a key role in enantioinduction. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.02.023

文献信息

• Substitution reactions between arenethiolate anions and 1,3-dihalo-2,2-dimethylpropanes. Synthetic scope and mechanistic aspects
  作者：Alicia Beatriz Peñéñory、Cecilia Andrea Barrionuevo、Juan Elias Argüello

  DOI：10.3998/ark.5550190.0012.721

  日期：——

  The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2-naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good to excellent yields. For all the substrates studied the monosubstituted halogenated product is the intermediate or the main product depending on the

  研究了苯硫醇、4-甲氧基苯硫醇、2-萘硫醇和2-吡啶硫醇阴离子与1,3-二卤-2,2-二甲基丙烷反应的合成范围。这些反应使单取代和二取代产物的产率从良好到极好。对于所有研究的底物，根据第二个离去基团的性质，单取代的卤化产物是中间体或主要产物。芳基环丙基硫化物被发现是副产物，它们的产率很大程度上取决于碱浓度 (tertBuOK)。最后，使用新戊基碘作为模型，基于非动力学证据评估了这些反应的机制，表明根据所使用的溶剂，反应从 SRN1 转换为极性 SN2。