Carbon Dot as Visible-Light Photoredox Catalysts for a Myriad of Organic Transformations.

Metal-free catalysts for various organic transformations are of high demand now. In this study, we present a new carbon dot as an efficient metal-free nanophotocatalyst for carrying out a series of organic bond formation reactions. Using a single photocatalyst carbon dot, Csp2-Csp2, Csp2-B, Csp2-S, Csp2-Se, and C-P bond formation reactions were performed with a high yield of the corresponding products. Moreover, Csp2-H activation of the aromatic ring was achieved by merging the carbon dot photocatalyst with a transition metal. Interestingly, these carbon nanodot-based catalysts show good recyclability a few times without any significant loss of catalytic activity. The development of catalytic systems based on carbon dots has its merits vested in the advantageous properties of this nanomaterial, such as a robust chemical nature and cheap cost of preparation. This report demonstrates that a carbon dot indeed holds the potential to replace expensive metal-based catalysts as well as organic dyes in five different photoredox reactions.

Enroute sustainability: metal free C-H bond functionalisation.

The term "C-H functionalisation" incorporates C-H activation followed by its transformation. In a single line, this can be defined as the conversion of carbon-hydrogen bonds into carbon-carbon or carbon-heteroatom bonds. The catalytic functionalisation of C-H bonds using transition metals has emerged as an atom-economical technique to engender new bonds without activated precursors which can be considered as a major drawback while attempting large-scale synthesis. Replacing the transition-metal-catalysed approach with a metal-free strategy significantly offers an alternative route that is not only inexpensive but also environmentally benign to functionalize C-H bonds. Recently metal free synthetic approaches have been flourishing to functionalize C-H bonds, motivated by the search for greener, cost-effective, and non-toxic catalysts. In this review, we will highlight the comprehensive and up-to-date discussion on recent examples of ground-breaking research on green and sustainable metal-free C-H bond functionalisation.

Transition Metal-Catalyzed C-H Functionalization Through Electrocatalysis.

Electrochemically promoted transition metal-catalyzed C-H functionalization has emerged as a promising area of research over the last few decades. However, development in this field is still at an early stage compared to traditional functionalization reactions using chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal-catalyzed C-H functionalization. From the standpoint of sustainability, environmental friendliness, and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom-economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal-electrocatalyzed C-H functionalization over the past decade and describes how the unique features of electricity enable metal-catalyzed C-H functionalization in an economic and sustainable way.

Benzylic Alcohol Oxidation using Copper Oxide/ZincOxide/Zirconia Nanocomposite Catalysts.

Herein, we have developed a nanocomposite catalyst for organic transformation. The catalysts are synthesized based on CuO/ZnO/ZrO2 materials through the coprecipitation method followed by calcination in air at 500 °C for 5 h. The physicochemical characterization using TGA, XRD, SEM and N2 -physisorption at -196 °C was carried out for all the prepared catalysts. Nanocomposite catalyst with Cu/Zn=1 : 1 showed the smallest particle size and largest surface area among all the other investigated catalysts. Under ideal reaction conditions, this new heterogenous catalyst has demonstrated its excellent efficacy for the oxidation of benzylic alcohol and can be successfully used in up to three catalytic cycles with little loss of catalytic activity.

Fuzzy-logic-based IoMT framework for COVID19 patient monitoring.

Smart healthcare is an integral part of a smart city, which provides real time and intelligent remote monitoring and tracking services to patients and elderly persons. In the era of an extraordinary public health crisis due to the spread of the novel coronavirus (2019-nCoV), which caused the deaths of millions and affected a multitude of people worldwide in different ways, the role of smart healthcare has become indispensable. Any modern method that allows for speedy and efficient monitoring of COVID19-affected patients could be highly beneficial to medical staff. Several smart-healthcare systems based on the Internet of Medical Things (IoMT) have attracted worldwide interest in their growing technical assistance in health services, notably in predicting, identifying and preventing, and their remote surveillance of most infectious diseases. In this paper, a real time health monitoring system for COVID19 patients based on edge computing and fuzzy logic technique is proposed. The proposed model makes use of the IoMT architecture to collect real time biological data (or health information) from the patients to monitor and analyze the health conditions of the infected patients and generates alert messages that are transmitted to the concerned parties such as relatives, medical staff and doctors to provide appropriate treatment in a timely fashion. The health data are collected through sensors attached to the patients and transmitted to the edge devices and cloud storage for further processing. The collected data are analyzed through fuzzy logic in edge devices to efficiently identify the risk status (such as low risk, moderate risk and high risk) of the COVID19 patients in real time. The proposed system is also associated with a mobile app that enables the continuous monitoring of the health status of the patients. Moreover, once alerted by the system about the high risk status of a patient, a doctor can fetch all the health records of the patient for a specified period, which can be utilized for a detailed clinical diagnosis.

Non-directed Pd-catalysed electrooxidative olefination of arenes.

The Fujiwara-Moritani reaction is a powerful tool for the olefination of arenes by Pd-catalysed C-H activation. However, the need for superstoichiometric amounts of toxic chemical oxidants makes the reaction unattractive from an environmental and atom-economical view. Herein, we report the first non-directed and regioselective olefination of simple arenes via an electrooxidative Fujiwara-Moritani reaction. The versatility of this operator-friendly approach was demonstrated by a broad substrate scope which includes arenes, heteroarenes and a variety of olefins. Electroanalytical studies suggest the involvement of a Pd(ii)/Pd(iv) catalytic cycle via a Pd(iii) intermediate.

Dual Ligand Enabled Nondirected C-H Chalcogenation of Arenes and Heteroarenes.

Chalcogenide motifs are present as principal moieties in a vast array of natural products and complex molecules. Till date, the construction of these chalcogen motifs has been restricted to either the use of directing groups or the employment of a large excess of electronically activated arenes, typically employed as a cosolvent. Despite being highly effective, these methods have their own limitations in the step economy and the deployment of an excess amount of arenes. Herein, we report the evolution of a catalytic system employing arene-limited, nondirected thioarylation of arenes and heteroarenes using a complimentary dual-ligand approach. The reaction is controlled by a combination of steric and electronic factors, and the utilization of a suitable ligand enables the generation of products on a complimentary spectrum to that generated by classical methods. The combination of ligands remains imperative in the reaction protocol with theoretical calculations pointing towards a monoprotected amino acid ligand being crucial in the concerted metalation deprotonation (CMD) mechanism by a characteristic [5,6]-palladacyclic transition state, while the pyridine moiety assists in the active catalyst species formation and product release. Combined experimental and computational mechanistic investigations point toward the C-H activation step being both regio- and rate-determining. Interestingly, oxidative addition of the diphenyl disulfide substrate is found to be unlikely, and an alternative transmetalation-like mechanism involving the Pd-Ag heterometallic complex is proposed to be operative.

Transition Metal Catalyst, Solvent, Base Free Synthesis of Diaryl Diselenides under Mechanical Ball Milling.

A convenient, efficient, and general procedure for the synthesis of diaryl diselenides has been developed by the reaction of aryl diazonium tetrafluoroborates and Potassium Selenocyanate on the surface of alumina under ball-milling in absence of any solvent, transition metal catalyst and base in room temperature. A wide range of functionalized diaryl diselenides are obtained in high purity and high yield by this procedure. BACKGROUND: Synthesis of diaryl diselenides was restricted into only few Cu-catalyzed C-Se Cross coupling protocol where use of ligands, high reaction temp, long reaction time were required. OBJECTIVE: To achieve a sustainable protocol for the synthesis of diaryl diselenides Method: Reaction of aryl diazonium fluoroborate with KSeCN was successfully performed under ball milling in absence of any ransition metal catalyst, ligands, base and external heating to get diaryl diselenides. RESULTS: A library of diaryl diselenides were obtained in good yields with different functional groups. CONCLUSION: First transition metal free protocol for the synthesis of diaryl diselenides has been developed successfully.

Recent Advances in the Nitration of Olefins.

Nitroolefins are important synthetic intermediates in the field of organic synthesis as well as in medicinal chemistry. The high reactivity of nitroalkenes due to the polarized double bond which enables them to act as Michael acceptor in conjugate addition reactions, or as a dienophile in cycloaddition makes it an essential synthetic handle for accessing complex molecules. The classical method to prepare nitroolefins is indeed the Henry nitroaldol reaction, where a carbonyl compound and nitroalkane are condensed in presence of base. Direct nitration of olefin, on the other hand, serves as a useful alternative as olefins are abundant, have broad commercial availability and easy to manipulate. In this context, numerous methods have been developed over the last few decades, focusing on direct nitration of styrene and aliphatic olefins. Furthermore, thorough literature search revealed that implementation of this class of reactions are gaining momentum as a preferred pathway to access nitroolefins, despite the presence of a powerful technique such as Henry reaction. In this review, we aim to cover recent advances in direct olefin nitration and their importance in accessing biorelevant molecules, total synthesis targets and future outlook in this specific research area.

Synergistic Effect of NiLDH@YZ Hybrid and Mechanochemical Agitation on Glaser Homocoupling Reaction.

Herein, we report the synthesis of nickel-layered double hydroxide amalgamated Y-zeolite (NiLDH@YZ) hybrids and the evaluation of the synergistic effect of various NiLDH@YZ catalysts and mechanochemical agitation on Glaser homocoupling reactions. Nitrogen adsorption-desorption experiments were carried out to estimate the surface area and porosity of NiLDH@YZ hybrids. The basicity and acidity of these hybrids were determined by CO2 -TPD and NH3 -TPD experiments respectively and this portrayed good acid-base bifunctional feature of the catalysts. The NiLDH@YZ-catalyzed mechanochemical Glaser coupling reaction achieved best yield of 83 % for the 0.5NiLDH@0.5YZ hybrid after 60 min of agitation, which revealed the highest acid-base bifunctional feature compared to all the investigated catalysts. The developed catalyst has proven itself as a robust and effective candidate that can successfully be employed up to four catalytic cycles without significant loss in catalytic activity, under optimized reaction conditions. This work demonstrated a new strategy for C-C bond formation enabled by the synergy between mechanochemistry and heterogeneous catalysis.

Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones.

Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.

Hydroboration of Alkynes with Zwitterionic Ruthenium-Borate Complexes: Novel Vinylborane Complexes.

Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido-[(Cp*Ru)2 B3 H9] (1) with other ligand systems was explored. In this regard, mild thermolysis of nido-1 with 2-mercaptobenzothiazole (2-mbzt), 2-mercaptobenzoxazole (2-mbzo) and 2-mercaptobenzimidazole (2-mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH3 L] (2 a-c) and ß-agostic complexes [Cp*RuBH2 L2] (3 a-c; 2 a, 3 a: L=C7 H4 NS2 ; 2 b, 3 b: L=C7 H4 NSO; 2 c, 3 c: L=C7 H5 N2 S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2 (CH2 )n PPh2 ] (n=1-3) yielded [Cp*Ru(PPh2 (CH2 )n PPh2 )-BH2 (L2)] (4 a-c; 4 a: n=1; 4 b: n=2; 4 c: n=3; L=C7 H4 NS2). Mild thermolysis of 2 a with [PPh2 (CH2)n PPh2 ] (n=1-3) led to the isolation of [Cp*Ru(PPh2 (CH2)n PPh2 )(L)] (L=C7 H4 NS2 5 a-c; 5 a: n=1; 5 b: n=2; 5 c: n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R-C=CH2 )BH(L2)] (6 and 7; 6: R=Ph; 7: R=COOCH3; L=C7 H4 NS2). Complexes 6 and 7 can also be viewed as η-alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds.