Lithium;2-methoxy-6-(4-methyl-2,6,7-trioxa-1-boranuidabicyclo[2.2.2]octan-1-yl)pyridine

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Lithium;2-methoxy-6-(4-methyl-2,6,7-trioxa-1-boranuidabicyclo[2.2.2]octan-1-yl)pyridine
• 英文别名: lithium;2-methoxy-6-(4-methyl-2,6,7-trioxa-1-boranuidabicyclo[2.2.2]octan-1-yl)pyridine
• 化学式: C₁₁H₁₅BNO₄*Li
• 分子量: 242.996
• InChiKey: DIHSTJWWAQORSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.68
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Lithium;2-methoxy-6-(4-methyl-2,6,7-trioxa-1-boranuidabicyclo[2.2.2]octan-1-yl)pyridine 、 四丁基氢氧化铵 以 甲醇 为溶剂， 反应 15.0h， 生成
  参考文献：
  名称：

  Tetrabutylammonium 2-Pyridyltriolborate Salts for Suzuki–Miyaura Cross-Coupling Reactions with Aryl Chlorides

  摘要：

  Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of tetrabutylammonium 2-pyridyltriolborate salts with various aryl (heteroaryl) chlorides can produce the corresponding desired coupling products with good to excellent yields. These tetrabutylammonium salts are more reactive than the corresponding lithium salts. The coupling reactions with aryl chlorides progressed in the presence of PdCl(2)dcpp (3 mol %) and Cul/MeNHCH2CH2OH (20 mol %) in anhydrous DMF without bases.

  DOI：

  10.1021/ol402268g
• 作为产物：
  描述：

  原乙酸三甲酯 、 2-溴-6-甲氧基吡啶 在 正丁基锂 、 硼酸三异丙酯 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 Lithium;2-methoxy-6-(4-methyl-2,6,7-trioxa-1-boranuidabicyclo[2.2.2]octan-1-yl)pyridine
  参考文献：
  名称：

  Tetrabutylammonium 2-Pyridyltriolborate Salts for Suzuki–Miyaura Cross-Coupling Reactions with Aryl Chlorides

  摘要：

  Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of tetrabutylammonium 2-pyridyltriolborate salts with various aryl (heteroaryl) chlorides can produce the corresponding desired coupling products with good to excellent yields. These tetrabutylammonium salts are more reactive than the corresponding lithium salts. The coupling reactions with aryl chlorides progressed in the presence of PdCl(2)dcpp (3 mol %) and Cul/MeNHCH2CH2OH (20 mol %) in anhydrous DMF without bases.

  DOI：

  10.1021/ol402268g

文献信息

• Rhodium-Catalyzed Asymmetric 1,4-Addition of Heteroaryl Cyclic Triolborate to α,β-Unsaturated Carbonyl Compounds
  作者：Yasunori Yamamoto、Norio Miyaura、Xiao-Qiang Yu

  DOI：10.1055/s-0028-1088198

  日期：2009.4

  Rhodium-catalyzed asymmetric 1,4-additions of electron-deficient heteroaryl groups to α,β-unsaturated carbonyl compounds were established. The reaction resulted in very low yields due to competitive C-B bond cleavage when arylboronic acids, their pinacol esters, or potassium trifluoroborates were used. However, the corresponding lithium heteroaryl(triol)borates afforded 1,4-adducts with high enantioselectivities up to 97% in the presence of a rhodium(I) catalyst chelated with a chiral BINAP or BIPAM ligand.

  铑催化的电子缺乏杂环芳基对α,β-不饱和羰基化合物的非对称1,4-加成反应已被建立。当使用芳基硼酸、其匹那可酯或三氟硼酸钾时，反应的产率非常低，原因是竞争性的C-B键断裂。然而，对应的锂杂环芳基（醇）硼酸盐在铑(I)催化剂与手性BINAP或BIPAM配体形成的配位状态下，能够提供高达97%的优异对映选择性1,4-加成产物。