2-methyl-1-indanone sodium salt | 1005350-78-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 2-methyl-1-indanone sodium salt
• 英文别名: sodium;2-methyl-3H-inden-1-olate
• CAS: 1005350-78-6
• 化学式: C₁₀H₉O*Na
• 分子量: 168.171
• InChiKey: AVGKTQJMICXZBI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.66
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-1-indanone sodium salt 、 [(R)-BINAP]Ni(Cl)(C6H4-4-CF3) 在 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以72%的产率得到(R)-2-methyl-2-(4-trifluoromethyl)-1-indanone
  参考文献：
  名称：

  Nickel-Catalyzed Asymmetric α-Arylation and Heteroarylation of Ketones with Chloroarenes: Effect of Halide on Selectivity, Oxidation State, and Room-Temperature Reactions

  摘要：

  We report the alpha-arylation of ketones with a range of aryl chlorides with enantioselectivities from 90 to 99% ee catalyzed by the combination of Ni(COD)(2) and (R)-BINAP and the coupling of ketones with a range of heteroaryl chlorides with enantioselectivities up to 99% ee catalyzed by Ni(COD)(2) and (R)-DIFLUORPHOS. The analogous reactions of bromoarenes occur with much lower enantioselectivities. Mechanistic studies showed that the difference in the rates of decomposition of the arylnickel(II) halide intermediates to {[(R)-BINAP]NiX}(2) likely accounts for the difference in the enantioselectivities of the reactions of bromoarenes and chloroarenes. This catalyst decomposition can be overcome by conducting the reactions with [(R)-BINAP]Ni(eta(2)-NC-Ph) (4), which undergoes oxidative addition to haloarenes at room temperature.

  DOI：

  10.1021/ja2082087

文献信息

• Enantioselective α-Arylation of Ketones with Aryl Triflates Catalyzed by Difluorphos Complexes of Palladium and Nickel
  作者：Xuebin Liao、Zhiqiang Weng、John F. Hartwig

  DOI：10.1021/ja074453g

  日期：2008.1.1

  90%. Systematic studies on these alpha-arylations have revealed a number of factors that affect enantioselectivity. Ligands containing biaryl backbones with smaller dihedral angles generate catalysts that react with higher enantioselectivity than related ligands with larger dihedral angles. In addition, faster rates for reactions of aryl triflates versus those for reactions of aryl bromides allow the

  描述了酮与芳基三氟甲磺酸酯的不对称 α-芳基化，并且该亲电子试剂与含有 segphos 衍生物的镍和钯催化剂的使用显着增加了酮烯醇化物的高度对映选择性芳基化的范围。芳基三氟甲磺酸酯作为反应物、二氟磷作为配体、用于电子中性或富电子芳基三氟甲磺酸酯反应的钯催化剂和用于缺电子芳基三氟甲磺酸酯反应的镍催化剂的组合导致了四氢萘酮、茚满酮的一系列α-芳基化、环戊酮和环己酮衍生物。对映选择性范围从 70% 到 98%，其中 10 个实例超过 90%。对这些 α-芳基化的系统研究揭示了许多影响对映选择性的因素。含有具有较小二面角的联芳基骨架的配体产生的催化剂比具有较大二面角的相关配体具有更高的对映选择性反应。此外，与芳基溴化物反应相比，芳基三氟甲磺酸酯的反应速率更快，允许芳基三氟甲磺酸酯的α-芳基化在较低温度下进行，并且该较低温度提高了对映选择性。最后，研究将催化反应的对映选择性与分离的 [(segpho