27644-00-4

Usage

Chemical Class

Aromatic ketones

Derivation

Derived from biphenyl and ethanone

Structure

Features a phenyl group attached to the second carbon atom of the ethanone backbone

Applications

a. Synthesis of pharmaceuticals (anti-inflammatory and analgesic drugs)
b. Production of fragrances and flavorings
c. Versatile intermediate in organic chemistry

Reactivity

Unique structure and reactivity make it a valuable component in the development of new chemical products and applications

Upstream product

• 2522-81-8 2-<(2,2-dimethylpropanoyl)oxy>-1-phenylethanone 
• 105123-35-1 2,4,6-tris([1,1'-biphenyl]-4-yl)boroxine 
• 591-50-4 iodobenzene 
• 31603-77-7 4-biphenylacetonitrile 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 1276111-26-2 [1,1′-biphenyl]-4-yl(mesityl)iodonium trifluoromethanesulfonate 
• 1591-31-7 4-iodo-biphenyl 
• 98-86-2 acetophenone 
• 93-58-3 benzoic acid methyl ester 
• 644-08-6 4-Methylbiphenyl 
• 6919-61-5 N-methoxy-N-methylbenzamide 
• 20383-28-2 N,N-diisopropyl benzamide 
• 100-59-4 phenylmagnesium chloride 
• 5728-52-9 (4-biphenylyl)acetic acid 

Downstream Products

• 149365-92-4 2-Biphenyl-4-yl-1-phenyl-ethylamine 
• 149365-94-6 (2-Biphenyl-4-yl-1-phenyl-ethyl)-(2,2-diethoxy-ethyl)-amine 
• 36803-53-9 1-([1,1′-biphenyl]-4-yl)-2-phenylethane-1,2-dione 
• 112553-57-8 2-phenyl-9,10-phenanthrenequinone 
• 1283117-21-4 5-(biphenyl-4-yl)-4-(3-ethoxy-4-hydroxy-5-nitrophenyl)-6-phenyl-3,4-dihydropyrimidin-2(1H)-one 
• 1416727-92-8 N-(2-(biphenyl-4-yl)-1-phenylethylidene)-4-methoxyaniline 
• 1416727-71-3 N-(2-(biphenyl-4-yl)-1-phenylethyl)-4-methoxyaniline 
• 302777-51-1 2-(4'-biphenylyl)-1-phenylpropanone hydrazone 
• 302777-49-7 2-([1,1′-biphenyl]-4-yl)-1-phenylpropan-1-one 

Relevant academic research and scientific papers

Benzylic Aroylation of Toluenes Mediated by a LiN(SiMe3)2/Cs+System

Chemoselective deprotonative functionalization of benzylic C-H bonds is challenging, because the arene ring contains multiple aromatic C(sp2)-H bonds, which can be competitively deprotonated and lead to selectivity issues. Recently it was found that bimetallic [MN(SiMe3)2 M = Li, Na]/Cs+ combinations exhibit excellent benzylic selectivity. Herein, is reported the first deprotonative addition of toluenes to Weinreb amides mediated by LiN(SiMe3)2/CsF for the synthesis of a diverse array of 2-arylacetophenones. Surprisingly, simple methyl benzoates also react with toluenes under similar conditions to form 2-arylacetophenones without double addition to give tertiary alcohol products. This finding greatly increases the practicality and impact of this chemistry. Some challenging substrates with respect to benzylic deprotonations, such as fluoro and methoxy substituted toluenes, are selectively transformed to 2-aryl acetophenones. The value of benzylic deprotonation of 3-fluorotoluene is demonstrated by the synthesis of a key intermediate in the preparation of Polmacoxib.

Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts

A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.

Benzylic aroylation of toluenes with unactivated tertiary benzamides promoted by directed ortho-lithiation

The deprotonative functionalization of toluenes, for their weak acidity, generally needs strong bases, thus leading to the requirement of harsh conditions and the generation of by-products. Direct nucleophilic acyl substitution reaction of amides with organometallic reagents could provide an ideal solution for ketone synthesis. However, the inert amides and highly reactive organometallic reagents bring great challenges for an efficient and selective synthetic approach. Herein, we reported an lithium diisopropylamide (LDA)-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides, providing a direct and efficient synthesis of various aryl benzyl ketones. This process features a kinetic deprotonative functionalization of toluenes with a readily available base LDA. Mechanism studies revealed that the directed ortho-lithiation of the tertiary benzamide with LDA promoted the benzylic kinetic deprotonation of toluene and triggered the nucleophilic acyl substitution reaction with the amide. [Figure not available: see fulltext.].

Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles

An efficient one-pot two-step procedure for the synthesis of unsymmetrical (hetero)aryl 1,2-diketones has been developed. The reaction proceeds through a palladium-catalyzed nucleophilic addition of potassium aryltrifluoroborates to aliphatic nitriles followed by a copper-catalyzed aerobic benzylic C–H oxygenation using molecular oxygen as a green oxidant. This represents the first example of the direct synthesis of unsymmetrical diaryl 1,2-diketones from arylacetonitriles. This method utilizes inexpensive, stable, nontoxic, and readily available starting materials, is highly effective in the presence of both electron-rich and electron-poor nitriles and aryltrifluoroborates, and tolerates a wide variety of functional groups. The synthetic utility of this transformation was shown by increasing the scale of the reaction and by carrying out the one-pot protocol for the preparation of quinoxaline and benzimidazole derivatives. A plausible reaction mechanism has also been proposed.

The ketene-surrogate coupling: Catalytic conversion of aryl iodides into aryl ketenes through ynol ethers

tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergo electrocyclic ring closure to yield hydroxynaphthalenes and quinolines.

Palladium-catalyzed mono-α-arylation of carbonyl-containing compounds with aryl halides using dalphos ligands

We report the extension and optimization of the [Pd(cinnamyl)Cl] 2/DalPhos catalyst system, previously found effective for the mono-α-arylation of acetone, to the mono-α-arylation of a variety of carbonyl-containing compounds with aryl halides and heteroaryl halides. Aryl methyl ketones, heteroaryl methyl ketones, propiophenones, malonates, and methoxyacetone can be α-arylated under relatively mild conditions and in good yields. We also report the limitations of the ligand/catalyst system towards other classes of carbonyl-containing compounds. We report the application of the [Pd(cinnamyl)Cl]2/DalPhos catalyst system, previously found effective for the mono-α-arylation of acetone, to the mono-α-arylation of a variety of carbonyl-containing compounds with aryl halides and heteroaryl halides.

Nickel-catalyzed intermolecular insertion of aryl iodides to nitriles: A novel method to synthesize arylketones

A novel procedure for the NiCl2(DME)/dppp/Zn system catalyzed intermolecular insertion of aryl iodides to nitriles was developed, which afforded variously substituted arylketone derivatives in moderate to good yields with tolerance of a wide variety of functional groups.

NOVEL DIHYDROPYRIMIDIN-2(1H)-ONE COMPOUNDS AS S-NITROSOGLUTATHIONE REDUCTASE INHIBITORS

The present invention is directed to novel dihydropyrimidin-2(1H)-one compounds useful as S-nitrosoglutathione reductase (GSNOR) inhibitors, pharmaceutical compositions comprising such compounds, and methods of making and using the same.

Arylation of α-pivaloxyl ketones with arylboronic reagents via Ni-catalyzed sp3 C-O activation

A Suzuki-Miyaura coupling of α-pivaloxyl ketones via Ni-catalyzed sp3 C-O activation to produce α-aryl ketones is developed. This study offers a convenient method to construct α-arylation products from readily available α-hydroxyl carbonyl compounds.

Engineering reactions in crystalline solids: Prediction of intramolecular carbene rearrangements

The unimolecular reactivity and stereoselectivity of four arylalkyl carbenes generated by a steady state irradiation of crystalline 1,2-diaryldiazopropanes were correctly predicted by taking advantage of known reaction trajectories applied to structures obtained by simple molecular mechanics calculations. It is suggested that the conformation of the diazo compound in the crystal determines the conformation of the carbene intermediate which is predisposed for a conformationally stereospecific 1,2-H shift. The results of irradiations of 1,2-diaryldiazoalkanes in crystalline media were compared with those obtained in solution and in amorphous solids. It was demonstrated that rigidity alone is not sufficient for carbene reactions to proceed with high stereoselectivity. (C) 2000 Published by Elsevier Science Ltd.