Ligand-Enabled Double γ-C(sp3 )-H Functionalization of Aliphatic Acids: One-Step Synthesis of γ-Arylated γ-Lactones.

γ-methylene C(sp3 )-H functionalization of linear free carboxylic acids remains a significant challenge. Here in we report a Pd(II)-catalyzed tandem γ-arylation and γ-lactonization of aliphatic acids enabled by a L,X-type CarboxPyridone ligand. A wide range of γ-arylated γ-lactones are synthesized in a single step from aliphatic acids in moderate to good yield. Arylated lactones can readily be converted into disubstituted tetrahydrofurans, a prominent scaffold amongst bioactive molecules.

Remote C-H Olefination of Heterocyclic Biaryls Enabled by Reversibly Bound Templates.

Remote C-H functionalization of heterocyclic biaryls will be of great importance in synthesis and medicinal chemistry. Through adjusting the geometric relationship of the directing atom and target C-H bonds, two new catalytic templates have been developed to enable the functionalization of the more hindered ortho-C-H bonds of heterobiaryls bearing directing heteroatom at the meta- or para-positions, affording unprecedented site-selectivity. The use of template chaperone also overcomes product inhibition and renders the directing templates catalytic. The utility of this protocol was demonstrated by olefination of heterocyclic biaryls with various substituents, overriding conventional steric and electronic effects. These ortho-C-H olefinated heterobiaryls are sterically hindered and can often be challenging to prepare through aryl-aryl coupling reactions.

Metal-catalysed C-H bond activation and borylation.

Transition metal-catalysed direct borylation of hydrocarbons via C-H bond activation has received a remarkable level of attention as a popular reaction in the synthesis of organoboron compounds owing to their synthetic versatility. While controlling the site-selectivity was one of the most challenging issues in these C-H borylation reactions, enormous efforts of several research groups proved instrumental in dealing with selectivity issues that presently reached an impressive level for both proximal and distal C-H bond borylation reactions. For example, in the case of ortho C-H bond borylation reactions, innovative methodologies have been developed either by the modification of the directing groups attached with the substrates or by creating new catalytic systems via the design of new ligand frameworks. Whereas meta and para selective C-H borylations remained a formidable challenge, numerous innovative concepts have been developed within a very short period of time by the development of new catalytic systems with the employment of various noncovalent interactions. Moreover, significant advancements have occurred for aliphatic C(sp3)-H borylations as well as enantioselective borylations. In this review article, we aim to discuss and summarize the different approaches and findings related to the development of directed proximal ortho, distal meta/para, aliphatic (racemic and enantioselective) borylation reactions since 2014. Additionally, considering the C-H borylation reaction as one of the most important mainstream reactions, various applications of this C-H borylation reaction toward the synthesis of natural products, therapeutics, and applications in materials chemistry will be summarized in the last part of this review article.

Iridium-Catalyzed Ligand-Controlled Remote para-Selective C-H Activation and Borylation of Twisted Aromatic Amides.

A method of para-selective borylation of aromatic amides is described. The borylation proceeded via an unprecedented substrate-ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa) that is different from the traditionally used ligand (dtbpy) for the C-H borylation reactions. The designed ligand framework (defa) has led to the development of a new type of catalytic system that shows excellent para selectivity for a range of aromatic amides. Moreover, the designed ligand has shown excellent reactivity and selectivity for a range of heterocyclic aromatic amides. The identification of key transition states and intermediates using the DFT computations associated with the three regio-isomeric pathways revealed that the most efficient catalytic pathway with the defa ligand leads to the para borylation while in the case of bpy the borylation at the para and meta sites compete.

Development of Intelligent Fault Diagnosis Technique of Rotary Machine Element Bearing: A Machine Learning Approach.

The bearing is an essential component of a rotating machine. Sudden failure of the bearing may cause an unwanted breakdown of the manufacturing plant. In this paper, an intelligent fault diagnosis technique was developed to diagnose various faults that occur in a deep groove ball bearing. An experimental setup was designed and developed to generate faulty data in various conditions, such as inner race fault, outer race fault, and cage fault, along with the healthy condition. The time waveform of raw vibration data generated from the system was transformed into a frequency spectrum using the fast Fourier transform (FFT) method. These FFT signals were analyzed to detect the defective bearing. Another significant contribution of this paper is the application of a machine learning (ML) algorithm to diagnose bearing faults. The support vector machine (SVM) was used as the primary algorithm. As the efficiency of SVM heavily depends on hyperparameter tuning and optimum feature selection, the particle swarm optimization (PSO) technique was used to improve the model performance. The classification accuracy obtained using SVM with a traditional grid search cross-validation (CV) optimizer was 92%, whereas the improved accuracy using the PSO-based SVM was found to be 93.9%. The developed model was also compared with other traditional ML techniques such as k-nearest neighbor (KNN), decision tree (DT), and linear discriminant analysis (LDA). In every case, the proposed model outperformed the existing algorithms.

Prediction of COVID-19 Cases from the Nexus of Air Quality and Meteorological Phenomena: Bangladesh Perspective.

An integrated approach was used to estimate the number of COVID-19 patients related to air quality and meteorological phenomena. Additionally, the air quality during pre-lockdown, lockdown, and post-lockdown stages of the COVID-19 pandemic was assessed to determine the effect of the infection containment measures taken in Bangladesh during the pandemic. The air quality was assessed based on measurements of nitrogen dioxide (NO2), sulfur dioxide (SO2), ozone (O3), carbon monoxide (CO), black carbon, particulate matter (PM2.5 and PM10), and aerosol optical depth. Time-averaged maps of these parameters have been generated from NASA's (National Aeronautics and Space Administration) website. Values of these parameters have also been collected from a continuous air monitoring station (CAMS) located in Bangladesh's north-western city Rajshahi. The comparison shows that lockdown during the pandemic has brought significant improvements in air quality. However, the improvement was not sustained, since rapid increases in the air pollutant concentrations were observed in the post-lockdown period. Furthermore, Pearson correlation coefficients between each air quality variable and the daily new COVID-19 case rates were calculated. Different meteorological variables during the same time periods were determined to observe the variation in Rajshahi city. Relationships of these variables with the case rates were also established. Additionally, statistical analyses of the obtained data have been conducted for the measured variables using the Kruskal-Wallis test to assess the differences in the observed data among the pre-lockdown, lockdown, and post-lockdown periods. Dunn's "Q" test was employed to test if the variables showed significance statistical difference during the Kruskal-Wallis test for pairwise comparisons. From the study, it has been observed that both meteorological variables and air quality parameters have significant relationship with daily new COVID-19 case rates. Both positive and negative associations of these parameters with the COVID-19 case rates have been observed. Very high air pollution has been observed in the post-lockdown period. Thus, it is recommended that appropriate authorities undertake corrective measures to protect the environment in cities with large populations. This study provides guidance for decision makers and health officials for future research and potentially reducing the spread of COVID-19.

Ir-catalyzed proximal and distal C-H borylation of arenes.

Over the past two decades, the C-H bond activation and functionalization reaction has been known as a prevailing method for the construction of carbon-carbon and carbon-heteroatom bonds using various transition metal catalysts. In this context, the iridium-catalyzed C-H bond activation and borylation reaction is one of the most valued methods. However, the major challenge in these borylation reactions is how to control the proximal (ortho) and distal (meta and para) selectivity. Interestingly, while so many approaches are now available for the proximal ortho selective borylation of arenes, borylation at the distal meta and or para position of arenes remains still challenging. Only a few approaches have been reported so far in the literature employing iridium catalysis. In this feature article, we have demonstrated some of the recent discoveries from our laboratories for the proximal (ortho) and distal (meta and para) selective borylation reactions. Moreover, some of the recent catalyst engineering discoveries for the selective proximal ortho borylation reactions for a diverse class of substrates have also been discussed. The discussion part of several other pioneering reports is limited due to the lack of scope of this feature article.

Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates.

Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.

Amide Effects in C-H Activation: Noncovalent Interactions with L-Shaped Ligand for meta Borylation of Aromatic Amides.

A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O⋅⋅⋅K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C-H activation/borylation.

Noncovalent Interactions in Ir-Catalyzed C-H Activation: L-Shaped Ligand for Para-Selective Borylation of Aromatic Esters.

An efficient strategy for the para-selective borylation of aromatic esters is described. For achieving high para-selectivity, a new catalytic system has been developed modifying the core structure of the bipyridine. It has been proposed that the L-shaped ligand is essential to recognize the functionality of the oxygen atom of the ester carbonyl group via noncovalent interaction, which provides an unprecedented controlling factor for para-selective C-H activation/borylation.