1-cyclopropyl-2-methyl-3-phenylpropan-1-one | 1262017-98-0

• 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: 1-cyclopropyl-2-methyl-3-phenylpropan-1-one
• CAS: 1262017-98-0
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: OSPMNLHFHVEQPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  2-benzylbi(cyclopropan)-1-ol 在 bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 作用下， 以 甲苯 为溶剂， 反应 18.0h， 以93%的产率得到1-cyclopropyl-2-methyl-3-phenylpropan-1-one
  参考文献：
  名称：

  Synthesis of α-methyl ketones by a selective, iridium-catalyzed cyclopropanol ring-opening reaction

  摘要：

  A mild method for synthesizing a-methyl ketones from substituted cyclopropanols is reported. This process, catalyzed by [Cp*IrCl2](2), cleaves cyclopropanol rings regioselectively and more efficiently than the other conditions examined. While tertiary cyclopropanols afford a-methyl ketones, secondary cyclopropanols and cyclopropyl silyl ethers are less reactive and yield other isomerization products. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.10.067

文献信息

• Rhodium-Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α-Branched Products
  作者：Louis K. M. Chan、Darren L. Poole、Di Shen、Mark P. Healy、Timothy J. Donohoe

  DOI：10.1002/anie.201307950

  日期：2014.1.13

  The rhodium‐catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen‐borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α‐branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a

  使用甲醇作为甲基化剂和借氢方法完成了铑催化的酮的甲基化。该序列的显着之处在于所需的温度相对较低，并且反应系统能够轻松形成 α 支化产物。双烷基化酮可以通过使用连续的一锅铱和铑催化工艺由甲基酮和两种不同的醇制备。
• Iron-Catalyzed Tandem Three-Component Alkylation: Access to α-Methylated Substituted Ketones
  作者：Léo Bettoni、Charlotte Seck、Mbaye Diagne Mbaye、Sylvain Gaillard、Jean-Luc Renaud

  DOI：10.1021/acs.orglett.9b00630

  日期：2019.5.3

  The borrowing hydrogen strategy has been applied in the synthesis of α-branched methylated ketones via a tandem three-component reaction catalyzed by a diaminocyclopentadienone iron tricarbonyl complex. Various alkyl and aromatic methyl ketones underwent dialkylation with various primary alcohols and methanol as alkylating agents in mild reaction conditions and good yields. Deuterium labeling experiments

  通过二氨基环戊二烯酮三羰基铁络合物催化的串联三组分反应，借位氢策略已应用于α-支化甲基化酮的合成中。各种烷基和芳族甲基酮在温和的反应条件下以良好的收率与各种伯醇和甲醇作为烷基化剂进行了二烷基化反应。氘标记实验表明，在串联过程中，苯甲醇是氢源。
• Utilization of MeOH as a C1 Building Block in Tandem Three-Component Coupling Reaction
  作者：Kaushik Chakrabarti、Milan Maji、Dibyajyoti Panja、Bhaskar Paul、Sujan Shee、Gourab Kanti Das、Sabuj Kundu

  DOI：10.1021/acs.orglett.7b02105

  日期：2017.9.15

  Ru(II) catalyzed tandem synthesis of α-branched methylated ketones via multicomponent reactions following the hydrogen borrowing process is described. This nonphosphine-based air and moisture stable catalyst efficiently produced various methylated ketones using methanol as a methylating agent. This system was found to be highly effective in three-component coupling between methanol, primary alcohols

  描述了Ru（II）在氢借位过程之后通过多组分反应催化串联合成α-支化甲基化酮。使用甲醇作为甲基化剂，这种基于非膦的空气和水分稳定的催化剂有效地生产了各种甲基化的酮。发现该系统在甲醇，伯醇和甲基酮之间的三组分偶联中非常有效。DFT计算和动力学实验支持了拟议的α-甲基化催化循环。
• Selective reductive α-methylation of chalcone derivatives using methanol
  作者：Anirban Sau、Dibyajyoti Panja、Sadhan Dey、Rahul Kundu、Sabuj Kundu

  DOI：10.1016/j.jcat.2022.08.035

  日期：2022.10

  An electron rich, new co-operative iridium(III) complex catalysed tandem conversion of α,β-unsaturated ketones to the α-methylated ketones is described using methanol. Employing this chemoselective protocol, reductive methylation of a wide range of chalcone derivatives, variety of aryl and aliphatic fragment containing α,β-unsaturated ketones along with few biologically important molecules were effectively

  使用甲醇描述了一种富电子的新型合作铱 (III) 配合物催化 α,β-不饱和酮到 α-甲基化酮的串联转化。采用这种化学选择性方案，有效地进行了广泛的查耳酮衍生物、各种芳基和脂肪族片段的还原甲基化，这些片段包含 α,β-不饱和酮以及一些生物学上重要的分子。完成了几个对照实验、动力学研究、Hammett 研究和 DFT 计算，以理解这种合作的铱 (III) 催化的 α,β-不饱和酮的串联还原甲基化。
• Well-Defined Bis(NHC)Mn(I) Complex Catalyzed Tandem Transformation of α,β-Unsaturated Ketones to α-Methylated Ketones Using Methanol
  作者：Kasturi Ganguli、Adarsha Mandal、Sabuj Kundu

  DOI：10.1021/acscatal.2c04131

  日期：2022.10.7

  Tandem transformation of α,β-unsaturated ketones to α-methylated ketones by utilizing methanol as both the hydrogen and C1 sources is reported in the presence of a phosphine-free bis-N-heterocyclic carbene-Mn(I) (bis-NHC-Mn(I)) catalyst. The dehydrogenative coupling between methanol and α,β-unsaturated ketones produces the corresponding α-methylated ketones along with 1 equiv of formaldehyde and water

  在无膦双-N-杂环卡宾-Mn(I) (bis-NHC- Mn(I)) 催化剂。甲醇和 α,β-不饱和酮之间的脱氢偶联产生相应的 α-甲基化酮以及 1 equiv 的甲醛和水。在不同的双-NHC-Mn(I) 配合物中，乙基翼尖取代的具有三氟甲磺酸根抗衡阴离子的配合物表现出最高的催化活性。该催化体系对于多种底物的还原甲基化非常有效，包括含有 α,β-不饱和酮的芳香族、杂芳香族和脂肪族直链底物。尤其，这种方法导致合成了药学上重要的药物分子，如乙哌立松和兰哌立松。进行了几个控制实验、动力学研究、Hammett 研究和密度泛函理论 (DFT) 计算以了解这种串联催化过程。