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• 10312-71-7 1,6-bis-(4-chlorophenyl)-3,4-diacetyl-1,5-hexazadiene 

Relevant academic research and scientific papers

N-Heterocyclic Carbene Ligand-Controlled Chemodivergent Suzuki-Miyaura Cross Coupling

Two N-heterocyclic carbene ligands provide orthogonal chemoselectivity during the Pd-catalyzed Suzuki-Miyaura (SM) cross-coupling of chloroaryl triflates. The use of SIPr [SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene] leads to selective cross-coupling at chloride, while the use of SIMes [SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] provides selective coupling at triflate. With most chloroaryl triflates and arylboronic acids, ligand-controlled selectivity is high (≥10:1). The scope of this methodology is significantly more general than previously reported methods for selective SM coupling of chloroaryl triflates using phosphine ligands. Density functional theory studies suggest that palladium's ligation state during oxidative addition is different with SIMes compared to SIPr.

Integrating Organic Lewis Acid and Redox Catalysis: The Phenalenyl Cation in Dual Role

In recent years, merging different types of catalysis in a single pot has drawn considerable attention and these catalytic processes have mainly relied upon metals. However, development of a completely metal free approach integrating organic redox and organic Lewis acidic property into a single system has been missing in the current literature. This study establishes that a redox active phenalenyl cation can activate one of the substrates by single electron transfer process while the same can activate the other substrate by a donor-acceptor type interaction using its Lewis acidity. This approach has successfully achieved light and metal-free catalytic C-H functionalization of unactivated arenes at ambient temperature (39 entries, including core moiety of a top-selling molecule boscalid), an economically attractive alternative to the rare metal-based multicatalysts process. A tandem approach involving trapping of reaction intermediates, spectroscopy along with density functional theory calculations unravels the dual role of phenalenyl cation.

Radical Arylation of Anilines and Pyrroles via Aryldiazotates

The radical arylation of anilines and pyrroles can be achieved under transition-metal- and catalyst-free conditions by using aryldiazotates in strongly alkaline aqueous solutions. The aryldiazotates act as protected diazonium ions, which do not undergo azo coupling with electron-rich aromatic substrates, but can still serve as an aryl radical source at slightly elevated temperatures. Based on an improved preparation of aryldiazotates in aqueous solution, homolytic aromatic substitutions of anilines and pyrroles were conducted with good overall yields and high regioselectivity. Moreover, DFT calculations provided further mechanistic insights.

Halogen selectivity in nickel salt-catalyzed cross-coupling of aryl Grignard reagents with bromochlorobenzenes - A novel synthetic method of unsymmetrical terphenyl

The reactions of aryl Grignard reagents with p- and m-bromochlorobenzenes catalyzed by non-ligated NiCl2 give selectively chlorobiphenyl derivatives. By the stepwise reaction, an unsymmetrical terphenyl was synthesized in a good yield.

Phase-Transfer-Catalyzed Gomberg-Bachmann Synthesis of Unsymmetrical Biarenes: A Survey of Catalysts and Substrates

Two problems have hindered the Gomberg-Bachmann (GB) and Pschorr reactions of arenediazonium cations: the instability of the arenediazonium salts and side reactions.Arenediazonium tetrafluoroborate and hexafluorophosphate salts can be prepared in high yield and purity and can be stored safely.Unfortunately, these salts are insoluble in most nonpolar organic solvents.Crown ether complexation or other phase-transfer (pt) catalytic methodology can ameliorate this situation, and reactions conducted by the approaches outlined herein often afforded coupling or cyclization products in high yield and corresponding purity.The use of crown ethers, quarternary 'onium salts, lipophilic carboxylic acid salts, and even the polar cosolvent acetonitrile increase the utility of the ptGB reaction dramatically.Sixty examples of couplings are reported along with an assessment of selectivities.A number of examples are also presented of phase-transfer-type Pschorr cyclizations.In the latter case, the use of potassium superoxide, KO2, is introduced to suppress indazole formation.

Aryl radicals from hexazadienes and tetrazenes

Aryl radicals are produced from both ends of the hexazadienes 1 and 2 and from the tetrazene 3, either thermally or photolytically.They attack aromatic compounds in the nucleus, the yield of biaryl being in the range 40-70percent, though it can be made nearly quantitative by using m-dinitrobenzene as additive.The aryl radicals also oxidize 2-propanol to acetone, the reaction products being the halogenobenzene and 1,2-diacetylhydrazine.Photolysis of 1 goes mainly by way of the tetrazene 3, and this may also be a significant pathway in the thermal reaction.Azodiacetylis an intermediate in the thermal reaction of 1 with 2-propanol and may be generally so in all its reactions.Radical induced decomposition is believed to be important in the reactions of 1, 2, and 3, and it is probably responsible for the formation of 1-acetyl-1-arylhydrazines, routinely produced in yields up to 25percent.