(R)-2-methyl-2-phenyl-2,3-dihydro-1H-inden-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (R)-2-methyl-2-phenyl-2,3-dihydro-1H-inden-1-one
• 英文别名: (R)-2-methyl-2-phenyl-1-indanone；(2R)-2-methyl-2-phenyl-3H-inden-1-one
• 化学式: C₁₆H₁₄O
• 分子量: 222.287
• InChiKey: CVZWTVDMZYGOSX-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (1-溴甲基-乙烯基)-苯 在 (S)-5-benzyl-2-(2,6-dimethoxyphenyl)-6,8-dihydro-5H-[1,2,4]triazolo[3,4-c][1,4]oxazin-2-ium tetrafluoroborate 、 magnesium 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 18.0h， 生成 (R)-2-methyl-2-phenyl-2,3-dihydro-1H-inden-1-one
  参考文献：
  名称：

  未活化烯烃的对映选择性分子内氢酰化：NHC催化的环状手性酮的稳健和多功能形成。

  摘要：

  高度对映选择性的分子内N杂环卡宾（NHC）催化的加氢酰化反应可从未活化的烯烃取代的醛（至多99％ee）中获得一系列环酮。值得注意的是，脂肪醛也首次在NHC催化的加氢酰化反应中得到了有效转化。

  DOI：

  10.1002/anie.201412302

文献信息

• Asymmetric Nanocatalysis: N-Heterocyclic Carbenes as Chiral Modifiers of Fe3O4/Pd nanoparticles
  作者：Kalluri V. S. Ranganath、Johannes Kloesges、Andreas H. Schäfer、Frank Glorius

  DOI：10.1002/anie.201002782

  日期：2010.10.11

  Superficial success: A chiral N‐heterocyclic carbene (NHC*) is used to modify Fe3O4/Pd nanoparticles, which then catalyze asymmetric α‐arylations. This successful synthesis of a heterogeneous catalyst and its appliation in asymmetric catalysis is in stark contrast to the simple immobilization of an established chiral homogeneous catalyst.

  表面上的成功：手性N-杂环卡宾（NHC *）用于修饰Fe 3 O 4 / Pd纳米粒子，然后催化不对称的α-芳基化。这种非均相催化剂的成功合成及其在不对称催化中的应用与已建立的手性均相催化剂的简单固定形成了鲜明的对比。
• 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
• Enantioselective α-Arylation of Cyclic Ketones Catalyzed by a Combination of an Unmodified Cinchona Alkaloid and a Palladium Complex
  作者：Christian Richter、Kalluri V. S. Ranganath、Frank Glorius

  DOI：10.1002/adsc.201100669

  日期：2012.2

  A palladium/Cinchona alkaloid-catalyzed α-arylation between cyclic ketones and aryl halides under phosphine-free conditions is presented. The use of a simple, unmodified Cinchona alkaloid results in high levels of activity and selectivity with up to 93% ee. These enantioinduction levels are comparable or even higher than the ones reported using palladium/BINAP complexes. To the best of our knowledge

  提出了在无膦条件下，环酮与芳基卤化物之间钯/金鸡纳生物碱催化的α-芳基化反应。使用简单的未经修饰的金鸡纳生物碱可导致高水平的活性和选择性，ee最高可达93％。这些对映体诱导水平与使用钯/ BINAP复合物所报道的对映体诱导水平相当或什至更高。据我们所知，这代表未修饰的金鸡纳生物碱在不对称过渡金属络合物催化的交叉偶联反应中首次用作配体/催化剂。
• Nickel-Catalyzed Asymmetric α-Arylation and Heteroarylation of Ketones with Chloroarenes: Effect of Halide on Selectivity, Oxidation State, and Room-Temperature Reactions
  作者：Shaozhong Ge、John F. Hartwig

  DOI：10.1021/ja2082087

  日期：2011.10.19

  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.
• Enantioselective Intramolecular Hydroacylation of Unactivated Alkenes: An NHC-Catalyzed Robust and Versatile Formation of Cyclic Chiral Ketones
  作者：Daniel Janssen-Müller、Michael Schedler、Mirco Fleige、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1002/anie.201412302

  日期：2015.10.12

  A highly enantioselective intramolecular N‐heterocyclic carbene (NHC)‐catalyzed hydroacylation reaction gives access to a range of cyclic ketones from unactivated olefin‐substituted aldehydes (up to 99 % ee). Remarkably, aliphatic aldehydes were also transformed efficiently in an NHC‐catalyzed hydroacylation reaction for the first time.

  高度对映选择性的分子内N杂环卡宾（NHC）催化的加氢酰化反应可从未活化的烯烃取代的醛（至多99％ee）中获得一系列环酮。值得注意的是，脂肪醛也首次在NHC催化的加氢酰化反应中得到了有效转化。