16216-08-3

Upstream product

• 90-11-9 1-Bromonaphthalene 
• 98-86-2 acetophenone 
• 90-13-1 1-Chloronaphthalene 
• 5121-00-6 naphthalen-1-yl-acetyl chloride 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 21792-52-9 1,2-diethynylbenzene 
• 140-29-4 phenylacetonitrile 
• 86-52-2 1-Chloromethylnaphthalene 
• 93-58-3 benzoic acid methyl ester 
• 90-12-0 1-Methylnaphthalene 
• 98-88-4 benzoyl chloride 
• 72867-71-1 N-(1-Cyano-2-naphthalen-1-yl-1-phenyl-ethyl)-N-phenyl-benzamide 
• 101733-67-9 2-amino-1-[1]naphthyl-1-phenyl-ethanol 
• 6919-61-5 N-methoxy-N-methylbenzamide 

Downstream Products

• 109692-15-1 5-[1]naphthyl-4-phenyl-thiazol-2-ylamine 
• 16216-09-4 2-(1-naphthyl)-1-phenylethanedione 
• 100188-75-8 3-phenyl-1,2-diazaphenanthrene 
• 33609-68-6 4-(naphthalen-1-yl)-2,5-diphenyl-1H-imidazole 
• 16216-10-7 3-[1]naphthyl-2,4,5-triphenyl-cyclopentadienone 
• 16303-53-0 2'--3'-phenyl-p-terphenyl 

Relevant academic research and scientific papers

Peri -Selective Direct Acylmethylation and Amidation of Naphthalene Derivatives Using Iridium and Rhodium Catalysts

An iridium-catalyzed acylmethylation and a rhodium-catalyzed amidation of naphthalene derivatives are reported, adopting sulfoxonium ylides and dioxazolones as carbene and nitrene transfer agents, respectively. The use of SMe group as a directing group was key to ensure the peri -selective functionalization, and it can be easily removed or diversely transformed to other synthetically useful functionalities after the catalysis.

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.

Electrochemical α-Arylation of Ketones via Anodic Oxidation of in Situ Generated Silyl Enol Ethers

An electrochemical procedure for the α-arylation of ketones has been developed. The method is based on the generation and one-pot anodic oxidation of silyl enol ethers in the presence of the arene. This strategy avoids isolation of the silyl enol intermediate and the utilization of external supporting electrolytes. Intermolecular arylations, which had not been reported so far, are possible when electron-rich arenes are utilized as coupling partners. The method has been demonstrated for a wide variety of aryl ketones and activated arenes, with moderate to good yields (up to 69%) obtained. Mechanistic insights and a theoretical rationale that explains the ketone α-arylation versus dimerization selectivity are also presented.

Iron-Catalyzed Enantioselective Radical Carboazidation and Diazidation of α,β-Unsaturated Carbonyl Compounds

Azidation of alkenes is an efficient protocol to synthesize organic azides which are important structural motifs in organic synthesis. Enantioselective radical azidation, as a useful strategy to install a C-N3 bond, remains challenging due to the inherently instability and unique structure of radicals. Here, we disclose an efficient enantioselective radical carboazidation and diazidation of α,β-unsaturated ketones and amides catalyzed by chiral N,N′-dioxide/Fe(OTf)2 complexes. An array of substituted alkenes was transformed to the corresponding α-azido carbonyl derivatives in good to excellent enantioselectivities, benefiting the preparation of chiral α-amino ketones, vicinal amino alcohols, and vicinal diamines. Control experiments and mechanistic studies proved the radical pathway in the reaction process. The DFT calculations showed that the azido transferred to the radical intermediate via an intramolecular five-membered transition state with the internal nitrogen of the Fe-N3 species.

Ruthenium(II)-Catalyzed Cross-Coupling of Benzoyl Formic Acids with Toluenes: Synthesis of 2-Phenylacetophenones

Herein, we report a direct method to synthesize 2-phenylacetophenone through a ruthenium(II)-catalyzed cross-coupling reaction between acyl and benzyl radical. The various derivatives of 2-phenylacetophenone were prepared easily in moderate to good yields. These reactions provide a straightforward pathway to synthesize a variety of ketones bearing various functional groups.

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.].

1,2-Aryl Migration Induced by Amide C?N Bond-Formation: Reaction of Alkyl Aryl Ketones with Primary Amines Towards α,α-Diaryl β,γ-Unsaturated γ-Lactams

Rearrangement reactions incorporated into cascade reactions play an important role in rapidly increasing molecular complexity from readily available starting materials. Reported here is a Cu-catalyzed cascade reaction of α-(hetero)aryl-substituted alkyl (hetero)aryl ketones with primary amines that incorporates an unusual 1,2-aryl migration induced by amide C?N bond formation to produce a class of structurally novel α,α-diaryl β,γ-unsaturated γ-lactams in generally good-to-excellent yields. This cascade reaction has a broad substrate scope with respect to primary amines, allows a wide spectrum of (hetero)aryl groups to smoothly undergo 1,2-migration, and tolerates electronically diverse α-substituents on the (hetero)aryl ring of the ketones. Mechanistically, this 1,2-aryl migration may stem from the intramolecular amide C?N bond formation which induces nucleophilic migration of the aryl group from the acyl carbon center to the electrophilic carbon center that is conjugated with the resulting iminium moiety.

N-heterocyclic carbene-palladium-imine complex catalyzed α-arylation of ketones with aryl and heteroaryl chlorides under air atmosphere

A new structure of saturated ring skeleton monoligated NHC-Pd-Imine complex was easily synthesized and unambiguously confirmed by X-ray single crystal diffraction. It was found to be an efficient and air-stable catalyst for the α-arylation of ketones. The reaction could be operated in air without any negative effect. Non-activated aryl and heteroaryl chlorides have been successfully applied in the reaction with only 0.5 mol% catalyst loadings under air atmosphere. Excellent to good product yields were afforded.

Aqueous α-Arylation of Mono- and Diarylethanone Enolates at Low Catalyst Loading

Acetophenone and deoxybenzoin derivatives are selectively α-arylated using a combination of very small amounts of palladium acetate and diphenylphosphine oxide as catalyst system and water as the only solvent. Target di- and triarylethanones are isolated virtually free of metal residues, and the reaction is amenable to gram-scale. A mechanistic proposal based on TEM images, poisoning experiments, kinetic plot and ESI-MS spectrometry is also provided. (Figure presented.).

Palladium-Catalyzed Ligand-Controlled Regioselective Nucleophilic Aromatic Substitution of 1-(Chloromethyl)naphthalenes with Arylacetonitriles

The palladium-catalyzed reaction of 1-(chloromethyl)naphthalenes 1 with (hetero)arylacetonitriles 2 gives either para- or ortho-acylated naphthalenes (3 or 4) in good to high yields. The regioselectivity can be controlled by the ligand of a palladium catalyst. A sterically bulky ligand, tBuPPh2, affords para-acylated products 3, whereas a sterically less bulky ligand, Me2PPh, provides ortho-acylated products 4. Further, direct substitution product 5 at the benzylic position is not obtained essentially, although such a reaction at the benzylic position is favorable in ordinary nucleophilic substitutions. In this paper, it was revealed that the benzylpalladium intermediate could react through a different mode (η3-benzylpalladium intermediate or η1-benzylpalladium intermediate) in nucleophilic aromatic substitution. In addition to the interesting mechanistic aspect, the present reaction provides a facile synthetic method for a wide range of diaryl ketones, some of which are not easily available through the previously known procedures.