An efficient approach to isoquinoline via AgNO3-promoted 6-endo-dig cyclization followed by oxidative elimination of o-alkynylarylaldimines and its application in fluoride recognition

A novel 6-endo-dig cyclization followed by oxidation/elimination of o-alkynylarylaldimines with 4-hydroxybenzylamine was developed for preparation of isoquinolines. The intermediates of this tandem reaction were monitored by mass spectroscopy (MS) to confirm the reaction pathway. This methodology was further applied to the design and synthesis of a novel ratiometric chemosensor for determination of fluoride.     

Evolution of weak noise and regular waves on dissipative shock fronts described by the Burgers model

The interaction of weak noise and regular signals with a shock wave having a finite width is studied in the framework of the Burgers equation model. The temporal realization of the random process located behind the front approaches it at supersonic speed. In the process of moving to the front, the intensity of noise decreases and the correlation time increases. In the central region of the shock front, noise reveals non-trivial behaviour. For large acoustic Reynolds numbers the average intensity can increase and reach a maximum value at a definite distance. The behaviour of statistical characteristics is studied using linearized Burgers equation with variable coefficients reducible to an autonomous equation. This model allows one to take into account not only the finite width of the front, but the attenuation and diverse character of initial profiles and spectra as well. Analytical solutions of this equation are derived. Interaction of regular signals of complex shape with the front is studied by numerical methods. Some illustrative examples of ongoing processes are given. Among possible applications, the controlling the spectra of signals, in particular, noise suppression by irradiating it with shocks or sawtooth waves can be mentioned.     

Singularities and spectral asymptotics of a random nonlinear wave in a nondispersive system

In this paper, we study the propagation of high-intensity acoustic noise in free space and in waveguide systems. A mathematical model generalizing the Burgers equation is used. It describes the nonlinear wave evolution inside tubes of variable cross-section, as well as in ray tubes, if the geometric approximation for heterogeneous media is used. The generalized equation transforms to the common Burgers equation with a dissipative parameter, known as the “Reynolds–Goldberg number”. In our model, this number depends on the distance travelled by the wave. With a zero “viscous” dissipative term, the model reduces to the Riemann (or Hopf) equation. Its solution presents the field by an implicit function. The spectral form of this solution makes it possible to derive explicit expressions for both dynamic and statistical characteristics of intense waves. The use of a spectral approach allowed us to describe the high-intensity noise in media with zero and finite viscosity. Applicability conditions of these solutions are defined. Since the phase matching is fulfilled for any triplet of interacting spectral components, there is an avalanche-like increase in the number of harmonics and the formation of shocks. The relationship between these discontinuities and other singularities and the high-frequency asymptotic of intense noise is studied. The possibility is shown to enhance nonlinear effects in waveguide systems during the evolution of noise.     

Exploring Regioselective Bond Cleavage and Cross‐Coupling Reactions using a Low‐Valent Nickel Complex

Recently, esters have received much attention as transmetalation partners for cross‐coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}₂(μ‐η²:η²‐C₆H₆)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η²‐carbonyl complexes. In contrast, acetylthioesters underwent rapid C_acyl?S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross‐coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η²‐carbonyl complex, phenyl esters were found to predominantly undergo C_aryl?O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2‐naphthyl acetate was also found to undergo clean C_aryl?O bond cleavage, and although stoichiometric cross‐coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.     

Mechanistic Insights into C(sp2)−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes

A new family of phosphine-ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary ^12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp²)−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp³)−C(sp³), C(sp²)−C(sp²), and C(sp³)−C(sp²) bond formation processes taking place on gold(III) species.     

Gold-Catalyzed Cross-Coupling Reactions: An Overview of Design Strategies,Mechanistic Studies,and Applications

Transition-metal-catalyzed cross-coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently, many studies have showed that both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions. Here, an overview of the past studies, current trends, and future directions in the field of gold-catalyzed coupling reactions is presented. Design strategies to accomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and experimental mechanistic studies, and their applications in diverse fields are critically reviewed. Specific topics covered are: oxidant-assisted and oxidant-free reactions; strain-assisted reactions; dual Au and photoredox catalysis; bimetallic synergistic reactions; mechanisms of reductive elimination processes; enzyme-mimicking Au chemistry; cluster and surface reactions; and plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au^I/Au^III chemistry are discussed and the predictions from the calculations are compared with the experimental observations to derive useful design strategies.     

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

Impact of N-Aryl- and NHC Core-Substituents on the Coupling of Alkylzinc Nucleophiles: Is Bigger always Better?

Bulky Pd−N-heterocyclic carbene (NHC) catalysts (e. g., N-(di-2,6-(3-pentyl)phenyl), IPent) have been shown to have significantly higher reactivity in a wide variety of cross-coupling applications (i. e., C−C, C−S, C−N) than less hindered variants (e. g., N-(di-2,6-(isopropyl)phenyl), IPr). Further, chlorinating the backbone of the NHC ring sees an even greater increase in reactivity. In the cross-coupling of (hetero)aryl electrophiles to secondary alkyl nucleophiles, making the N-aryl groups larger reduces the amount of β-hydride elimination leading to alkene byproducts and chlorinating the NHC core had an even greater effect, all but eliminating alkene formation. In the present study involving the cross-coupling of primary alkyl electrophiles and nucleophiles, a sharp and surprising reversal of all of the above trends was observed. Bulkier catalysts had generally slower rate of reaction and β-hydride elimination worsened leading to extensive amounts of alkene byproducts.     

Click Chemistry on Polymer Support: Synthesis of 1-Vinyl- and 1-Allyl-1,2,3-triazoles via Selenium Linker

Polystyrene-supported 2-azidoethyl phenyl selenide and 3-azidopropyl phenyl selenide reagents have been developed and applied to the traceless solid-phase organic synthesis of 1-vinyl- and 1-allyl-1,2,3-triazoles by CuI-mediated azide–alkyne cycloadditions and subsequent cleavage from the polymer support through oxidation–elimination reaction with 30% hydrogen peroxide. The advantages of this method include straightforward operation, good yield and purity of the products, and good stability and lack of odor for the reagents.     

In Situ Solid‐State Generation of (BN)2‐Pyrenes and Electroluminescent Devices

New BN‐heterocyclic compounds have been found to undergo double arene photoelimination, forming rare yellow fluorescent BN‐pyrenes that contain two B? N units. Most significant is the discovery that the double arene elimination can also be driven by excitons generated electrically within electroluminescent (EL) devices, enabling the in situ solid‐state conversion of BN‐heterocycles to BN‐pyrenes and the use of BN‐pyrenes as emitters for EL devices. The in situ exciton‐driven elimination (EDE) phenomenon has also been observed for other BN‐heterocycles.