[Li(2,6-bis(oxazolinyl)phenyl)] | 847456-93-3

• 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: [Li(2,6-bis(oxazolinyl)phenyl)]
• CAS: 847456-93-3
• 化学式: C₁₆H₁₉N₂O₂*Li
• 分子量: 278.28
• InChiKey: HUYHBZNWTMOZPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.22
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Li(2,6-bis(oxazolinyl)phenyl)] 、 4,4'-bis[P-(chlorogold(I))diphenylphosphino]biphenyl 以 甲苯 为溶剂， 以93%的产率得到[(Au(2,6-bis(oxazolinyl)phenyl))2(4,4'-bis(diphenylphosphino)biphenyl)]
  参考文献：
  名称：

  A new, easily recyclable arylating agent based on a diphosphino-digold(i) complex

  摘要：

  本文介绍了两种有机金（I）配合物 [(Au(NCN))2(dppbp)] (6) 和 [(Au(Phebox))2(dppbp)] (9) 的合成及其在随后的反金属化反应中的应用。报告还介绍了一种三核有机金（I）配合物[(AuCl)3(tdpppb)] (4)，它在二氯甲烷中的溶解度之高令人惊讶。研究发现，6 和 9 可以分别将阴离子 NCN-（[C6H3(CH2NMe2)2-2,6]-）或 Phebox-（[2,6-双（恶唑啉基）苯基]-）分子干净地转移到 TiIV 和 PdII 中心。在这一跨金属化反应中形成的副产物[(AuCl)2(dppbp)]（3，dppbp 为 [4-Ph2PC6H4]2 (1)）几乎定量地从反应混合物（甲苯）中析出，因此只需简单过滤即可分离。相比之下，在[Au(NCN)(PPh3)]与金属盐的反金属反应中形成的副产物[AuCl(PPh3)]在非极性溶剂中的溶解度较高，因此更难从生成的有机金属复合物中分离出来。Digold 复合物 6 已通过核磁共振光谱和晶体学分析进行了表征。这些分析表明，两个金单元基本上是独立的。以金（I）为基础形成的二金属透金属剂对其透金属特性没有影响。

  DOI：

  10.1039/b701271c
• 作为产物：
  描述：

  1,3-bis(4,4-dimethyl-2-oxazoline-2-yl)benzene 在 正丁基锂 、 四甲基乙二胺 作用下， 生成 [Li(2,6-bis(oxazolinyl)phenyl)]
  参考文献：
  名称：

  n-Butyllithium/N,N,N‘,N‘-Tetramethylethylenediamine-Mediated Ortholithiations of Aryl Oxazolines:  Substrate-Dependent Mechanisms

  摘要：

  n-Butyllithium/N,N,N',N'-tetramethylethylenediamine-mediated ortholithiations of aryloxazolines are described. Methyl substituents on the aryloxazoline and substituents at the meta position of the arenes (methoxy, oxazolinyl, and fluoro) influence the rates and the mechanisms. Monomer- and dimer-based reactions are implicated. Density functional calculations probe details of the mechanism and suggest the origins of cooperative effects in meta-substituted aryl oxazolines.

  DOI：

  10.1021/ja068057u

文献信息

• n-Butyllithium/<i>N,N,N</i>‘<i>,N</i>‘-Tetramethylethylenediamine-Mediated Ortholithiations of Aryl Oxazolines:  Substrate-Dependent Mechanisms
  作者：Scott T. Chadwick、Antonio Ramirez、Lekha Gupta、David B. Collum

  DOI：10.1021/ja068057u

  日期：2007.2.1

  n-Butyllithium/N,N,N',N'-tetramethylethylenediamine-mediated ortholithiations of aryloxazolines are described. Methyl substituents on the aryloxazoline and substituents at the meta position of the arenes (methoxy, oxazolinyl, and fluoro) influence the rates and the mechanisms. Monomer- and dimer-based reactions are implicated. Density functional calculations probe details of the mechanism and suggest the origins of cooperative effects in meta-substituted aryl oxazolines.
• HARRIS T. D.; NEUSCHWANDER B.; BOEKELHEIDE V., J. ORG. CHEM. <JOCE-AH>, 1978, 43, NO 4, 727-730
  作者：HARRIS T. D.、 NEUSCHWANDER B.、 BOEKELHEIDE V.

  DOI：——

  日期：——
• Lithium Diisopropylamide-Mediated Ortholithiations: Lithium Chloride Catalysis
  作者：Lekha Gupta、Alexander C. Hoepker、Kanwal J. Singh、David B. Collum

  DOI：10.1021/jo802713y

  日期：2009.3.6

  Ortholithiations of a range of arenes mediated by lithium dilsopropylamide (LDA) in THF at -78 degrees C reveal substantial accelerations by as little as 0.5 mol % of LiCl (relative to LDA). Substrate dependencies suggest a specific range of reactivity within which the LiCl catalysis is optimal. Standard protocols with unpurified commercial samples of n-butyllithium to prepare LDA or commercially available LDA show marked batch-dependent rates-up to 100-fold-that could prove significant to the unwary practitioner. Other lithium salts elicit more modest accelerations. The mechanism is not discussed.
• A new, easily recyclable arylating agent based on a diphosphino-digold(i) complex
  作者：Marianne Stol、Dennis J. M. Snelders、Huub Kooijman、Anthony L. Spek、Gerard P. M. van Klink、Gerard van Koten

  DOI：10.1039/b701271c

  日期：——

  The synthesis of two organogold(I) complexes, [(Au(NCN))2(dppbp)] (6) and [(Au(Phebox))2(dppbp)] (9), and their application in subsequent transmetalating reactions are described. A trinuclear organogold(I) complex, [(AuCl)3(tdpppb)] (4) is also reported, which exhibits a surprisingly high solubility in dichloromethane. It was found that 6 and 9 can cleanly transfer the anionic NCN-([C6H3(CH2NMe2)2-2,6]−) or Phebox-([2,6-bis(oxazolinyl)phenyl]−) moiety to TiIV and PdII centers, respectively. The coproduct [(AuCl)2(dppbp)] (3, dppbp is [4-Ph2PC6H4]2 (1)) formed during this transmetalation reaction, precipitates almost quantitatively from the reaction mixture (toluene) and can thus be separated by simple filtration. In comparison, [AuCl(PPh3)], formed as the coproduct in the transmetalation reaction of [Au(NCN)(PPh3)] with metal salts, has a higher solubility in apolar solvents and thus is more difficult to separate from the resultant organometallic complex. Digold complex 6 has been characterized by NMR spectroscopy and crystallographic analyses. These analyses show that the two gold units are essentially independent. The formation of a dimetallic transmetalating agent based on gold(I) had no effect on its transmetalating properties.

  本文介绍了两种有机金（I）配合物 [(Au(NCN))2(dppbp)] (6) 和 [(Au(Phebox))2(dppbp)] (9) 的合成及其在随后的反金属化反应中的应用。报告还介绍了一种三核有机金（I）配合物[(AuCl)3(tdpppb)] (4)，它在二氯甲烷中的溶解度之高令人惊讶。研究发现，6 和 9 可以分别将阴离子 NCN-（[C6H3(CH2NMe2)2-2,6]-）或 Phebox-（[2,6-双（恶唑啉基）苯基]-）分子干净地转移到 TiIV 和 PdII 中心。在这一跨金属化反应中形成的副产物[(AuCl)2(dppbp)]（3，dppbp 为 [4-Ph2PC6H4]2 (1)）几乎定量地从反应混合物（甲苯）中析出，因此只需简单过滤即可分离。相比之下，在[Au(NCN)(PPh3)]与金属盐的反金属反应中形成的副产物[AuCl(PPh3)]在非极性溶剂中的溶解度较高，因此更难从生成的有机金属复合物中分离出来。Digold 复合物 6 已通过核磁共振光谱和晶体学分析进行了表征。这些分析表明，两个金单元基本上是独立的。以金（I）为基础形成的二金属透金属剂对其透金属特性没有影响。