Catalytic acceptorless dehydrogenative borylation of styrenes enabled by a molecularly defined manganese complex.

In this study, we employed a 3d metal complex as a catalyst to synthesize alkenyl boronate esters through the dehydrogenative coupling of styrenes and pinacolborane. The process generates hydrogen gas as the sole byproduct without requiring an acceptor, rendering it environmentally friendly and atom-efficient. This methodology demonstrated exceptional selectivity for dehydrogenative borylation over direct hydroboration. Additionally, it exhibited a preference for borylating aromatic alkenes over aliphatic ones. Notably, derivatives of natural products and bioactive molecules successfully underwent diversification using this approach. The alkenyl boronate esters served as precursors for the synthesis of various pharmaceuticals and potential anticancer agents. Our research involved comprehensive experimental and computational studies to elucidate the reaction pathway, highlighting the B-H bond cleavage as the rate-determining step. The catalyst's success was attributed to the hemilability and metal-ligand bifunctionality of the ligand backbone.

DFT-Guided Mechanistic Insights into Chemodivergence: A Mixed Explicit-Implicit Solvent Description to Dictate the Chemoselectivity.

Herein we report a density functional theory (DFT)-guided mechanistic investigation of the nitrile reduction reaction, which exhibits a solvent-dependent chemodivergence. This study reveals an interesting mechanistic picture, highlighting the exact role of a protic solvent, isopropanol, in regulating the reaction outcome. The explicit solvent effect involving polar protic isopropanol favors imine metathesis by proton hopping through stepwise addition and elimination steps and thus produces a secondary amine as the final product. In contrast, the nonpolar solvent n-hexane is incapable of facilitating the proton migration and stops the solvent-assisted imine metathesis. As a result, only primary amines are obtained as the final product. This DFT study provides a recipe for the choice of solvents that can dictate chemoselectivity in product formation.

Super-Reducing Behavior of Benzo[b]phenothiazine Anion Under Visible-Light Photoredox Condition.

Herein we describe the anion of benzo[b]phenothiazine as a super reductant species upon excitation by visible light. In contrary to N-substituted phenothiazines or benzophenothiazines, this molecule holds extreme reducing power to promote single electron transfer-based reductive cleavage at a potential of -3.51 V vs SCE. As a proof, a plethora of aryl chloride substrates have been reductively cleaved to fabricate molecules of the class isoindolinone and oxindole. Moreover, an aryl-chloride bond has been homolytically cleaved to generate aryl radicals that have been utilized for C-C cross-coupling or C-P bond formation reactions. To prove its extreme reducing ability, some of the aryl fluoride bonds have been cleaved to generate aryl radicals. A detailed photophysical study including steady-state and time-resolved spectroscopic techniques explain the molecule's behavior upon light excitation, and that correlates with its reactivity pattern. Theoretical calculations disclose the benzophenothiazine anion to be slightly puckered at the ground state as the molecule is antiaromatic in nature. In contrast, the excited-state geometry is planar, which is also close to that of the intermediate after one electron transfer. Abating the antiaromaticity of the anionic species is partially responsible for its highly reducing behavior.

A 2-Anilidomethylpyridine Ligand Framework Showcasing Hydride Storage and Transfer Abilities in Its Aluminum Chemistry.

Dearomatized 1,4-dihydropyridyl motifs are significant in both chemistry and biology for their potential abilities to deliver the stored hydride, driven by rearomatization. Biological cofactors like nicotinamide adenine dinucleotide (NADH) and organic 'hydride sources' like Hantzsch esters are prime examples. An organoaluminum chemistry on a 2-anilidomethylpyridine framework is reported, where such hydride storage and transfer abilities are displayed by the ligand's pyridyl unit. The pyridylmethylaniline proligand (NN LH) is simultaneously deprotonated and 1,4-hydroaluminated by AlH3 (NMe2 Et) to [(NN Lde )AlH(NMe2 Et)] (1; NN Lde =hydride-inserted dearomatized version of NN L). A hydride abstraction by B(C6 F5 )3 rearomatizes the pyridyl moiety to give the cationic aluminum hydride [(NN L)AlH(NMe2 Et)][HB(C6 F5 )3 ] (6). Notably, such chemical non-innocence is priorly unseen in this established ligand class. The hydroalumination mechanism is investigated by isolating the intermediate [(NN L)AlH2 ] (2) and by control experiments, and is also analyzed by DFT calculation. The results advocate an intriguing 'self-promoting' pathway, which underlines alane's Lewis acid/Brønsted base duality. NMe2 Et carrying the alane also plays a crucial role. In contrast, the chemistry between NN LH and AlMe3 is much different, giving only [(NN L)AlMe2 ] (4) from the adduct [(NN LH)AlMe3 ] (3) by deprotonation but not a subsequent pyridyl dearomatization in the presence or absence of NMe2 Et. This divergence is also justified by DFT analyses.

A Donor-Acceptor Cyclopropane by Intramolecular C(sp3)-H Activation at a Cyclic(alkyl)(amino)carbene Center and Its Fascinating Ring-Opening Chemistry.

Virtually irreversible intramolecular C-H activations are deleterious for aza-carbenes. A picolyl-tethered cyclic(alkyl)(amino)carbene (CAAC) isomerizes into a donor-acceptor cyclopropane in this manner but restores the CAAC status by retro-C-H activation in the presence of trapping agents like Se or CuCl. The same DA cyclopropane is readily hydrolyzed to a pyrrolidin-2-ol that acts as another picoCAAC precursor by undergoing 1,1-dehydration in the presence of Se or CuCl. The chemistry is distinct from the N-heterocyclic carbene analogue throughout.

Redox noninnocence of the formazanate ligand applied to catalytic formation of α-ketoamides.

The formazan ligands have been investigated as redox-noninnocent backbones for a long time. Despite their well-established behaviour as redox reservoirs, the demonstration of catalytic efficiency governed by redox noninnocence remains elusive. We report an iron-formazanate molecule for efficiently preparing α-keto amides, where a crucial reductive cleavage of the substrate molecule is tightly regulated by the electron donation from the formazanate, in a reversible manner.

Ligand-redox assisted nickel catalysis toward stereoselective synthesis of (n+1)-membered cycloalkanes from 1,n-diols with methyl ketones.

A well-defined, bench-stable nickel catalyst is presented here, that can facilitate double alkylation of a methyl ketone to realize a wide variety of cycloalkanes. The performance of the catalyst depends on the ligand redox process comprising an azo-hydrazo couple. The source of the bis electrophile in this double alkylation is a 1,n-diol, so that (n+1)-membered cycloalkanes can be furnished in a stereoselective manner. The reaction follows a cascade of dehydrogenation/hydrogenation reactions and adopts a borrowing hydrogen (BH) method. A thorough mechanistic analysis including the interception of key radical intermediates and DFT calculations supports the ligand radical-mediated dehydrogenation and hydrogenation reactions, which is quite rare in BH chemistry. In particular, this radical-promoted hydrogenation is distinctly different from conventional hydrogenations involving a metal hydride and complementary to the ubiquitous two-electron driven dehydrogenation/hydrogenation reactions.

Pyrazole-Mediated C-H Functionalization of Arene and Heteroarenes for Aryl-(Hetero)aryl Cross-Coupling Reactions.

Herein we introduce a transition-metal-free protocol that involves a commercially available, inexpensive pyrazole molecule to conduct C-C cross-coupling reactions at room temperature via a radical pathway. Using this method, an aryldiazonium salt has been coupled to a wide range of arenes and heteroarenes including benzene, mesitylene, thiophene, furan, benzoxazole to result the corresponding biaryl products. The full reaction mechanism is elucidated along with the crystallographic probation of an active initiator species. A potassium-stabilized deprotonated pyrazole steers single-electron transfer to the substrate and behaves as an initiator for the reaction.

Effect of Soil Type and Temperature on Persistence and Dissipation Kinetics of a New Readymix Formulation of Fomesafen + Quizalofop-ethyl.

The research portrays the fate of a new herbicide mixture of fomesafen and quizalofop-ethyl. The soil samples viz. red lateritic soil (A), coastal saline soil (B) and black soil (C) were fortified separately for fomesafen and quizalofop-ethyl at 0.5 (T1) and 1.0 mg kg-1 (T2) doses and incubated at 20, 30 and 40°C. A satisfactory mean recovery, precision and linearity proved that the methods were accurate. Both the herbicides followed first + first order kinetics. Higher persistence of fomesafen was observed in Soil C than Soil B and Soil A with 22.38-53.75 days half-life, whereas quizalofop-ethyl showed higher stability in Soil A than Soils B and C with half-life of 0.93-12.07 days. Both compounds showed faster rates of dissipation at increased temperature, irrespective of soil type. The current study will help to predict the effect of temperature on the dissipation of herbicides in different soil under real field scenario.

Effect of pH on the Hydrolytic Transformation of a New Mixture Formulation of Fomesafen and Quizalofop-ethyl in Water.

A hydrolytic transformation study was conducted in water of pH 4.0, 7.0 and 9.2 to evaluate the effect of pH on persistence of a new readymix formulation of fomesafen and quizalofop-ethyl. The water samples were fortified at 0.5 and 1 µg mL-1 levels and analysed at 0 (2 h), 1, 3, 7, 15, 30, 60, 90, 120, 150 days interval. Both the analytical methods were validated following SANTE guideline and found accurate based on average recovery of 80-100%, Relative standard deviation (RSD) < 20% and Coefficient of Determination (R2) 0.99. The dissipation of both the molecules was pH dependent and followed first order kinetics. Higher persistence of fomesafen was observed in alkaline pH as compared to neutral and acidic pH with half-life of 41.56-63.24 days, whereas higher stability of quizalofop-ethyl was observed in the water of acidic pH followed by neutral and alkaline pH with half-life of 1.26-8.09 days.

Validation of a Multiresidue Method for the Analysis of 86 Multiclass Pesticides in Litchi Fruit by Gas Chromatography-Tandem Mass Spectrometry.

BACKGROUND: Although India is an important producer of litchi fruit, there is hardly any validated method available for its pesticide residue analysis. This strongly warrants the need to standardize a simple multiresidue analytical method for efficient analysis of multiclass pesticides with specificity, sensitivity, and accuracy in a single chromatographic run in combination with MS determination. OBJECTIVE: The aim of this study was to develop and validate a rapid ethyl-acetate-based sample preparation method for a simultaneous determination of 86 pesticides in litchi fruit by using GC-tandem MS. METHODS: The method involved ethyl acetate as an extracting solvent and a combined salt system comprising sodium chloride and sodium sulphate for the organic layer separation. To obtain satisfactory recovery percentage of each pesticide studied here, this combination was selected for further validation based on selectivity, sensitivity, linearity, precision, and accuracy values. RESULTS: The correlation coefficient (r2) of studied pesticides ranged between 0.97 and 0.99 at six concentration levels from 5 to 250 ng/mL. Furthermore, the average recovery values were within 70 and 120%, with repeatability relative SD below 20% for all 86 pesticides at the LOQ level and with an appreciable Horwitz ratio distribution that ranged between 0.5 and 2. CONCLUSIONS: All data demonstrate that the proposed method is adequately linear, accurate, and repeatable. Therefore, it can be widely used in commercial laboratories for analyzing pesticide residues for both domestic and export purposes. The method is in support of protecting consumer health. HIGHLIGHTS: A large-scale multiresidue method is reported for simultaneous analysis of a wide range of pesticides in litchi. The method complies with the regulatory requirements in terms of sensitivity for maximum residue limit compliance. The performance of the method complied with the SANTE guidelines of analytical QC.

Nondestructive Analysis of Debonds in a Composite Structure under Variable Temperature Conditions.

This paper presents a nondestructive analysis of debonds in an adhesively-bonded carbon-fibre reinforced composite structure under variable temperature conditions. Towards this, ultrasonic guided wave propagation based experimental analysis and numerical simulations are carried out for a sample composite structure to investigate the wave propagation characteristics and detect debonds under variable operating temperature conditions. The analysis revealed that the presence of debonds in the structure significantly reduces the wave mode amplitudes, and this effect further increases with the increase in ambient temperature and debond size. Based on the debond induced differential amplitude phenomenon, an online monitoring strategy is proposed that directly uses the guided wave signals from the distributed piezoelectric sensor network to localize the hidden debonds in the structure. Debond index maps generated from the proposed monitoring strategy show the debond identification potential in the adhesively-bonded composite structure. The accuracy of the monitoring strategy is successfully verified with non-contact active infrared-thermography analysis results. The effectiveness of the proposed monitoring strategy is further investigated for the variable debond size and ambient temperature conditions. The study establishes the potential for using the proposed damage index constructed from the differential guided wave signal features as a basis for localization and characterization of debond damages in operational composite structures.

Adaptivity in Bayesian Inverse Finite Element Problems: Learning and Simultaneous Control of Discretisation and Sampling Errors.

The local size of computational grids used in partial differential equation (PDE)-based probabilistic inverse problems can have a tremendous impact on the numerical results. As a consequence, numerical model identification procedures used in structural or material engineering may yield erroneous, mesh-dependent result. In this work, we attempt to connect the field of adaptive methods for deterministic and forward probabilistic finite-element (FE) simulations and the field of FE-based Bayesian inference. In particular, our target setting is that of exact inference, whereby complex posterior distributions are to be sampled using advanced Markov Chain Monte Carlo (MCMC) algorithms. Our proposal is for the mesh refinement to be performed in a goal-oriented manner. We assume that we are interested in a finite subset of quantities of interest (QoI) such as a combination of latent uncertain parameters and/or quantities to be drawn from the posterior predictive distribution. Next, we evaluate the quality of an approximate inversion with respect to these quantities. This is done by running two chains in parallel: (i) the approximate chain and (ii) an enhanced chain whereby the approximate likelihood function is corrected using an efficient deterministic error estimate of the error introduced by the spatial discretisation of the PDE of interest. One particularly interesting feature of the proposed approach is that no user-defined tolerance is required for the quality of the QoIs, as opposed to the deterministic error estimation setting. This is because our trust in the model, and therefore a good measure for our requirement in terms of accuracy, is fully encoded in the prior. We merely need to ensure that the finite element approximation does not impact the posterior distributions of QoIs by a prohibitively large amount. We will also propose a technique to control the error introduced by the MCMC sampler, and demonstrate the validity of the combined mesh and algorithmic quality control strategy.

Active control of transmission loss with smart foams.

Smart foams combine the complimentary advantages of passive foam material and spatially distributed piezoelectric actuator embedded in it for active noise control applications. In this paper, the problem of improving the transmission loss of smart foams using active control strategies has been investigated both numerically and experimentally inside a waveguide under the condition of plane wave propagation. The finite element simulation of a coupled noise control system has been undertaken with three different smart foam designs and their effectiveness in cancelling the transmitted wave downstream of the smart foam have been studied. The simulation results provide insight into the physical phenomenon of active noise cancellation and explain the impact of the smart foam designs on the optimal active control results. Experimental studies aimed at implementing the real-time control for transmission loss optimization have been performed using the classical single input/single output filtered-reference least mean squares algorithm. The active control results with broadband and single frequency primary source inputs demonstrate a good improvement in the transmission loss of the smart foams. The study gives a comparative description of the transmission and absorption control problems in light of the modification of the vibration response of the piezoelectric actuator under active control.