Deuterium-Labeling Studies on the C–H/Olefin Coupling of Aromatic Ketones Catalyzed by Fe(PMe3)4

Synthesis ◽  
2021 ◽  
Author(s):  
Fumitoshi Kakiuchi ◽  
Naoki Kimura ◽  
Shiori Katta ◽  
Yoichi Kitazawa ◽  
Takuya Kochi
Keyword(s):  
Aromatic Ketone ◽  
Deuterium Labeling ◽  
Aromatic Ketones ◽  
Olefin Coupling

AbstractDeuterium-labeling experiments were performed for the Fe(PMe3)4-catalyzed C–H/olefin coupling using a deuterium-labeled aromatic ketone with various alkenes. While the reactions with a variety of alkenes provided the linear alkylation products formed via 1,2-insertion of alkene into an Fe–H bond, the reversible 2,1-insertion proceeded during the reaction highly depends on the choice of the alkene. No H/D scrambling resulting from 2,1-insertion/β-elimination was detected for the reactions with a vinylsilane and N-vinylcarbazole, but the reactions­ with styrenes are considered to involve rapid 2,1-insertion/ β-elimination processes to cause significant levels of H/D scrambling.

A Facile One-pot Synthesis of Substituted Quinolines via Cascade Friedlander Reaction from Isoxazoles with Ammonium Formate-Pd/C and Ketones

2020 ◽  
Vol 17 (3) ◽  
pp. 211-215
Author(s):  
Da Chen ◽  
Xuan Wang ◽  
Runnan Wang ◽  
Yao Zhan ◽  
Xiaohan Peng ◽  
...  
Keyword(s):  
Hydrogen Transfer ◽  
Ammonium Formate ◽  
Aromatic Ketone ◽  
Reaction Conditions ◽  
One Pot ◽  
Diverse Range ◽  
Strong Base ◽  
Aromatic Ketones ◽  
Substituted Quinolines ◽  
New Strategy

The Friedlander reaction is the most commonly used method to synthesis substituted quinolines, the essential intermediates in the medicine industry. A facile one-pot approach for synthesizing substituted quinolines by the reaction of isoxazoles, ammonium formate-Pd/C, concentrated sulfuric acid, methanol and ketones using Friedlander reaction conditions is reported. Procedures for the synthesis of quinoline derivatives were optimized, and the yield was up to 90.4%. The yield of aromatic ketones bearing electron-withdrawing groups was better than the ones with electron-donating substituents. The structures of eight substituted quinolines were characterized by MS, IR, H-NMR and 13CNMR, which were in agreement with the expected structures. The mechanism for the conversion was proposed, which involved the Pd/C catalytic hydrogen transfer reduction of unsaturated five-membered ring of isoxazole to produce ortho-amino aromatic ketones. Then the nucleophilic addition of with carbonyl of the ketones generated Schiff base in situ, which underwent an intermolecular aldol reaction followed by the elimination of H2O to give production of substituted quinolines. This new strategy can be readily applied for the construction of quinolines utilizing a diverse range of ketones and avoids the post-reaction separation of the o-amino aromatic ketone compounds. The conventionally used o-amino aromatic ketone compounds in Friedlander reaction to prepare substituted quinoline are laborious to synthesize and are apt to self-polymerize. While oxazole adopted in this work can be prepared at ease by the condensation of benzoacetonitrile and nitrobenzene derivatives under the catalysis of a strong base. Moreover, the key features of this protocol are readily available starting materials, excellent functional group tolerance, mild reaction conditions, operational simplicity, and feasibility for scaling up.

Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution

2015 ◽  
Vol 17 (29) ◽  
pp. 19247-19254 ◽  
Author(s):  
Shu-Feng Zhao ◽  
Mike Horne ◽  
Alan M. Bond ◽  
Jie Zhang
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Electrochemical Reduction ◽  
Product Distribution ◽  
Aromatic Ketone ◽  
Aromatic Ketones ◽  
Bulk Electrolysis ◽  
Electrolysis Product

The yield of electrocarboxylation of aromatic ketone depends on the imidazolium-based ionic liquid anion and the ketone substituent.

Butenolide annelation using a manganese(III) oxidation. A synthesis of chromolaenin (Laevigatin)

1999 ◽  
Vol 77 (8) ◽  
pp. 1336-1339 ◽  
Author(s):  
Ayhan S Demir ◽  
Zuhal Gercek ◽  
Nese Duygu ◽  
A Cigdem Igdir ◽  
Omer Reis
Keyword(s):  
Aromatic Ketone ◽  
Arbuzov Reaction ◽  
Acetate Oxidation ◽  
Aromatic Ketones

A procedure was developed for the annelation of a butenolide to an aromatic ketone that highlighted a manganese(III) oxidation of an aromatic ketone. The merit of this procedure was illustrated in a synthesis of Chromolaenin (Laevigatin) (1) from 4,7-dimethyl-1-tetralone (2c). Oxidation of tetralone and indanone with manganese(III) acetate in the presence of chloro- or bromopropionic acid or their Mn(II) salts furnished a α-haloesters 3a-d. An Arbuzov reaction of haloesters with triethylphosphite and an intramolecular Horner-Watsworth-Emmons cyclization of the resulting phosphonate gave butenolide 5a, b in 77-79% yield. This methodology was also applied to 4,7-dimethyl-1-tetralone (2c), and the corresponding butenolide 6 is synthesized in 85% yield, which was then converted to Chromolaenin (1) using DIBAL-H.Key words: chromolaenin (Laevigatin), manganese(III) acetate oxidation, aromatic ketones, butenolide annelation, lactone, Horner-Watsworth-Emmons cyclization, Arbuzov reaction.

Selective α,α-Dibromination of Arylethanones with Copper(II) Bromide

2019 ◽  
Vol 16 (9) ◽  
pp. 700-704
Author(s):  
Jitander K. Kapoor ◽  
Loveena Arora ◽  
Om Prakash
Keyword(s):  
Ethyl Acetate ◽  
Heterogeneous System ◽  
Side Chain ◽  
Selective Synthesis ◽  
Aromatic Ketones

Various arylethanones including electron-rich aromatic ketones such as o-hydroxyacetophenone and its p-isomer underwent selective side-chain α,α-dibromination using a heterogeneous system consisting of four molar equivalents of copper(II) bromide in chloroform-ethyl acetate under reflux. This study provides the cleanest method for the selective synthesis of several synthetically useful α,α-dibromoketones which are otherwise difficult to prepare.

l-Prolinal Dithioacetal: A Highly Effective Organocatalyst for the Direct Nitro-Michael Addition to Selected Cyclic and Aromatic Ketones

Synthesis ◽  
2019 ◽  
Vol 51 (17) ◽  
pp. 3356-3368
Author(s):  
Piotr Pomarański ◽  
Zbigniew Czarnocki
Keyword(s):  
Michael Addition ◽  
Ring Size ◽  
Cyclic Ketones ◽  
Asymmetric Syntheses ◽  
Aromatic Ketones ◽  
Ring Systems ◽  
Effective Catalyst ◽  
Acetophenone Derivatives ◽  
Highly Effective ◽  
Related Compounds

The synthesis of novel l-prolinal dithioacetal and its application as an organocatalyst for the direct Michael addition of cyclic ketones and acetophenone derivatives to trans-β-nitrostyrene and related compounds is described. The prolinal dithioacetal acts as effective catalyst in the case of cyclic ketones of different ring size, in particular five- and six-membered examples, as well as larger and smaller ring systems. High enantioselectivity and diastereoselectivity is observed for different substrates and trans-β-nitrostyrenes. Also, the first asymmetric syntheses of selected 2-methyl-4-nitro-1,3-diphenylbutan-1-one derivatives by application of the obtained organocatalyst is presented.

The Merger of CF3SO2Na and Palladium Catalysis to Enable Decarboxylative Cross-Coupling for the Synthesis of Aromatic Ketones under Room Temperature

2021 ◽  
Author(s):  
Pan Xie ◽  
Cheng Xue ◽  
Cancan Wang ◽  
Dongdong Du ◽  
Sanshan Shi
Keyword(s):  
Visible Light ◽  
Room Temperature ◽  
Palladium Catalysis ◽  
Cross Coupling ◽  
Boronic Acids ◽  
Aromatic Ketones ◽  
Aryl Ketones ◽  
Oxocarboxylic Acids

A CF3SO2Na/Pd(OAc)2 co-catalyzed strategy is developed to produce aryl ketones via visible-light-induced decarboxylative cross-coupling of α-oxocarboxylic acids and aryl boronic acids. This process was perfomed under air at room temperature,...

Iron-Catalyzed Ortho C–H Homoallylation of Aromatic Ketones with Methylenecyclopropanes

2021 ◽  
Author(s):  
Naoki Kimura ◽  
Shiori Katta ◽  
Yoichi Kitazawa ◽  
Takuya Kochi ◽  
Fumitoshi Kakiuchi
Keyword(s):  
Aromatic Ketones

scholarly journals Esterifications with 2-(Trimethylsilyl)ethyl 2,2,2-Trichloroacetimidate

Organics ◽  
2021 ◽  
Vol 2 (1) ◽  
pp. 17-25
Author(s):  
Wenhong Lin ◽  
Shea T. Meyer ◽  
Shawn Dormann ◽  
John D. Chisholm
Keyword(s):  
Carboxylic Acid ◽  
High Yield ◽  
Deuterium Labeling ◽  
Ester Formation ◽  
Acid Substrate

2-(Trimethylsilyl)ethyl 2,2,2-trichloroacetimidate is readily synthesized from 2-trimethylsilylethanol in high yield. This imidate is an effective reagent for the formation of 2-trimethylsilylethyl esters without the need for an exogenous promoter or catalyst, as the carboxylic acid substrate is acidic enough to promote ester formation without an additive. A deuterium labeling study indicated that a β-silyl carbocation intermediate is involved in the transformation.

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