Ligand-Controlled Copper-Catalyzed Halo-Halodifluoromethylation of Alkenes and Alkynes Using Fluorinated Carboxylic Anhydrides.

Polyhalogenated molecules are often found as bioactive compounds in nature and are used as synthetic building blocks. Fluoroalkyl compounds hold promise for the development of novel pharmaceuticals and agrochemicals, as the introduction of fluoroalkyl groups is known to improve lipophilicity, membrane permeability, and metabolic stability. Three-component 1,2-halo-halodifluoromethylation reactions of alkenes are useful for their synthesis. However, general methods enabling the introduction of halodifluoromethyl (CF2X) and halogen (X') groups in the desired combination of X and X' are lacking. To address this gap, for the first time, we report a three-component halo-halodifluoromethylation of alkenes and alkynes using combinations of commercially available fluorinated carboxylic anhydrides ((CF2XCO)2O, X=Cl and Br) and alkali metal halides (X'=Cl and Br). In situ prepared fluorinated diacyl peroxides were identified as important intermediates, and the use of appropriate bipyridyl-based ligands and a copper catalyst was essential for achieving high product selectivity. The synthetic utility of the polyhalogenated products was demonstrated by exploiting differences in the reactivities of their C-X and C-X' bonds to achieve selective derivatization. Finally, the reaction mechanism and ligand effect were investigated using experimental and theoretical methods to provide important insights for the further development of catalytic reactions.

Recent advances in reactions using diacyl peroxides as sources of O- and C-functional groups.

Diacyl peroxides, (RCO2)2, are readily available and widely used reagents for organic synthesis, because they can serve as electrophiles, oxidants, and radical sources. Recently, they have been used extensively as sources of O- and C-functional groups, in contrast to their classical applications as radical initiators. These novel reaction modes have greatly expanded the synthetic utility of diacyl peroxides by making it possible to simultaneously utilize plural functionalities of diacyl peroxides in unprecedented ways, with or without the aid of transition-metal catalysts. Here, we review recent advances in reactions utilizing diacyl peroxides as O- and C-sources, with examples illustrating how the reactivity of diacyl peroxides in organic reactions can be controlled.

NHC-Catalyzed Desymmetrization of N-Aryl Maleimides Leading to the Atroposelective Synthesis of N-Aryl Succinimides.

Although the construction of axially chiral C-C bonds leading to the atroposelective synthesis of biaryls and allied compounds are well-known, the related synthesis of compounds bearing axially chiral C-N bonds are relatively rare. Described herein is the N-heterocyclic carbene-catalyzed atroposelective synthesis of N-aryl succinimides having an axially chiral C-N bond via the desymmetrization of N-aryl maleimides. The NHC involved intermolecular Stetter-aldol cascade of dialdehydes with prochiral N-aryl maleimides followed by oxidation afforded N-aryl succinimides in good yields and ee values. Preliminary studies on rotation barrier for the C-N bond, the temperature dependence, and detailed DFT studies on mechanism are also provided.

NHC-Catalyzed Generation of α,ß-Unsaturated Acylazoliums for the Enantioselective Synthesis of Heterocycles and Carbocycles.

This Account is aimed at highlighting the recent developments in the N-heterocyclic carbene (NHC)-catalyzed generation of α,ß-unsaturated acylazolium intermediates and their subsequent reactivity with (bis)nucleophiles thereby shedding light on the power of this NHC-bound intermediate in organocatalysis. This key intermediate can be generated by the addition of NHCs to α,ß-unsaturated aldehyde or acid derivatives. A wide variety of bisnucleophiles can add across the α,ß-unsaturated acylazoliums to form various five and six-membered heterocycles and carbocycles. Moreover, suitably substituted nucleophiles can add to this intermediate and result in valuable products following cascade processes. Employing chiral NHCs in the process can result in the enantioselective synthesis of valuable compounds. In 2013, we developed a unified strategy for the enantioselective synthesis of dihydropyranones and dihydropyridinones by the NHC-catalyzed formal [3 + 3] annulation of 2-bromoenals with readily available 1,3-dicarbonyl compounds or primary vinylogous amides. This reaction takes place under mild conditions with low catalyst loading. Interestingly, employing enolizable aldehydes as the bisnucleophiles in this annulation afforded chiral 4,5-disubstituted dihydropyranones in spite of the competing benzoin/Stetter pathways. Moreover, the use of cyclic 1,3-dicarbonyl compounds such as 4-hydroxy coumarin/pyrazolone afforded the coumarin/pyrazole-fused dihydropyranones. In addition, a [3 + 2] annulation for the synthesis of spiro γ-butyrolactones was demonstrated using 3-hydroxy oxindoles as the bisnucleophile. The interception of α,ß-unsaturated acylazolium intermediates with malonic ester derivatives having a γ-benzoyl group resulted in the enantioselective synthesis of functionalized cyclopentenes via a cascade process involving a Michael-intramolecular aldol-ß-lactonization-decarboxylation sequence. The use of cyclic ß-ketoamides as the coupling partner for catalytically generated α,ß-unsaturated acylazoliums resulted in the enantioselective synthesis of spiro-glutarimide and the reaction proceeds in a Michael addition-intramolecular amidation pathway. We have recently demonstrated the enantioselective synthesis of tricyclic δ-lactones with three contiguous stereocenters by the reaction of enals with dinitrotoluene derivatives bearing electron-withdrawing groups, under oxidative conditions. This atom-economic cascade reaction proceeds in a Michael/Michael/lactonization sequence tolerating a range of functional groups. This technique was also used for the N-H functionalization of indoles for the enantioselective synthesis of pyrroloquinolines following the aza-Michael/Michael/lactonization sequence. The use of α-arylidene pyrazolinones as the bisnucleophiles for the tandem generation of dienolate/enolates combined with the NHC-catalyzed generation of α,ß-unsaturated acylazoliums resulted in the enantioselective synthesis of pyrazolone-fused spirocyclohexadienones. This formal [3 + 3] annulation proceeds via the vinylogous Michael/spiroannulation/dehydrogenation sequence to afford spirocyclic compounds with an all-carbon quaternary stereocenter. It is reasonable to believe that the chemistry of α,ß-unsaturated acylazoliums, catalytically generated through NHCs, will continue to flourish and will lead to amazing results. Future challenges in this area include the applications of this key intermediate in the synthesis of biologically active natural products and drugs.

N-Heterocyclic Carbene-Catalyzed Formal [6+2] Annulation Reaction via Cross-Conjugated Aza-Trienolate Intermediates.

The diverse reactivity of N-heterocyclic carbenes (NHCs) in organocatalysis is due to the possibility of different modes of action. Although NHC-bound enolates and dienolates are known, the related NHC-bound cross-conjugated aza-trienolates remain elusive. Herein, we demonstrate the NHC-catalyzed formal [6+2] annulation of nitrogen-containing heterocyclic aldehydes with α,α,α-trifluoroacetophenones leading to the formation of versatile pyrrolooxazolones (29 examples). The catalytically generated cross-conjugated aza-trienolates (aza-fulvene type) underwent smooth [6+2] annulation with electrophilic ketones to afford the product in moderate to good yields under mild conditions. Preliminary DFT studies on the mechanism are also provided.

Synthesis of 2-Aryl Naphthoquinones by the Cross-Dehydrogenative Coupling Involving an NHC-Catalyzed endo-Stetter Reaction.

An N-heterocyclic carbene (NHC)-catalyzed intramolecular Stetter reaction proceeding via the endo-fashion was the key step for the transition-metal-free and mild cross-dehydrogenative coupling of 2-cinnamoyl benzaldehydes allowing for the synthesis of 2-aryl naphthoquinones. In this transformation, the carbene generated from the triazolium salt using Na2CO3 catalyzes the intramolecular Stetter reaction, which was followed by air oxidation to reinstall the C-C double bond.

Navigation Algorithm Based on the Boundary Line of Tillage Soil Combined with Guided Filtering and Improved Anti-Noise Morphology.

An improved anti-noise morphology vision navigation algorithm is proposed for intelligent tractor tillage in a complex agricultural field environment. At first, the two key steps of guided filtering and improved anti-noise morphology navigation line extraction were addressed in detail. Then, the experiments were carried out in order to verify the effectiveness and advancement of the presented algorithm. Finally, the optimal template and its application condition were studied for improving the image-processing speed. The comparison experiment results show that the YCbCr color space has minimum time consumption of 0.094   s in comparison with HSV, HIS, and 2R-G-B color spaces. The guided filtering method can effectively distinguish the boundary between the tillage soil compared to other competing vanilla methods such as Tarel, multi-scale retinex, wavelet-based retinex, and homomorphic filtering in spite of having the fastest processing speed of 0.113   s . The extracted soil boundary line of the improved anti-noise morphology algorithm has the best precision and speed compared to other operators such as Sobel, Roberts, Prewitt, and Log. After comparing different sizes of image templates, the optimal template with the size of 140   ×   260 pixels could achieve high-precision vision navigation while the course deviation angle was not more than 7.5 ° . The maximum tractor speed of the optimal template and global template were 51.41   km / h and 27.47   km / h , respectively, which can meet the real-time vision navigation requirement of the smart tractor tillage operation in the field. The experimental vision navigation results demonstrated the feasibility of the autonomous vision navigation for tractor tillage operation in the field using the tillage soil boundary line extracted by the proposed improved anti-noise morphology algorithm, which has broad application prospect.

Enantioselective Synthesis of Functionalized ß-Lactones by NHC-Catalyzed Aldol Lactonization of Ketoacids.

N-Heterocyclic carbene (NHC)-catalyzed intramolecular aldol lactonization of readily available ketoacids leading to the enantioselective synthesis of cyclopentane-fused ß-lactones is presented. The reaction proceeds via the generation of NHC-bound enolate intermediates formed from the ketoacids in the presence of the peptide coupling reagent HATU and NHC generated from the chiral triazolium salt. The functionalized ß-lactones are formed under mild conditions in high yields and enantioselectivities.

Enantioselective synthesis of spiro γ-butyrolactones by N-heterocyclic carbene (NHC)-catalyzed formal [3 + 2] annulation of enals with 3-hydroxy oxindoles.

The N-heterocyclic carbene (NHC)-catalyzed enantioselective formal [3 + 2] annulation of α,ß-unsaturated aldehydes with 3-hydroxy oxindoles is presented. Under oxidative conditions using the bisquinone oxidant, the reaction resulted in the synthesis of spiro γ-butyrolactones in moderate to good yields, enantioselectivity and diastereoselectivity. The reaction likely proceeds via the generation of the NHC-bound α,ß-unsaturated acylazolium intermediate from enals, which was intercepted by the dioxindoles in a formal [3 + 2] pathway to form the spirocyclic compounds. However, a deeper mechanistic investigation revealed that the reaction can also proceed via the homoenolate intermediate. In this case, the dioxindole was oxidized to the corresponding isatin derivative using traces of air under basic conditions, and was intercepted with the NHC-bound homoenolate intermediate in a formal [3 + 2] pathway to afford the spiro compound.

N-Heterocyclic-Carbene-Catalyzed Umpolung of Imines.

N-Heterocyclic carbene (NHC) catalysis has been widely used for the umpolung of aldehydes, and recently for the umpolung of Michael acceptors. Described herein is the umpolung of aldimines catalyzed by NHCs, and the reaction likely proceeds via aza-Breslow intermediates. The NHC-catalyzed intramolecular cyclization of aldimines bearing a Michael acceptor resulted in the formation of biologically important 2-(hetero)aryl indole 3-acetic-acid derivatives in moderate to good yields. The carbene generated from the bicyclic triazolium salt was found to be efficient for this transformation.

Enantioselective Synthesis of Spirocyclohexadienones by NHC-Catalyzed Formal [3+3] Annulation Reaction of Enals.

The enantioselective synthesis of pyrazolone-fused spirocyclohexadienones was demonstrated by the reaction of α,ß-unsaturated aldehydes with α-arylidene pyrazolinones under oxidative N-heterocyclic carbene (NHC)catalysis. This atom-economic and formal [3+3] annulation reaction proceeds through a vinylogous Michael addition/spiroannulation/dehydrogenation cascade to afford spirocyclic compounds with an all-carbon quaternary stereocenter in moderate to good yields and excellent ee values. Key to the success of the reaction is the cooperative NHC-catalyzed generation of chiral α,ß-unsaturated acyl azoliums from enals, and base-mediated tandem generation of dienolate/enolate intermediates from pyrazolinones.

Mechanical and Bioactive Properties of PMMA Bone Cement: A Review.

Over the past few decades, poly(methyl methacrylate) (PMMA) based bone cement has been clinically used extensively in orthopedics for arthroplasty and kyphoplasty, due to its biocompatibility and excellent primary fixation to the host bone. In this focused review, we discuss the use of various fillers and secondary chemical moieties to improve the bioactivity and the physicochemical properties. The viscosity of the PMMA blend formulations and working time are crucial to achieving intimate contact with the osseous tissue, which is highly sensitive to organic or inorganic fillers. Hydroxyapatite as a reinforcement resulted in compromised mechanical properties of the modified cement. The possible mechanisms of the additive- or filler-dependent strengthening or weakening of the PMMA blend are critically reviewed. The addition of layered double hydroxides with surface functionalization appears to be a promising approach to enhance the bonding of filler with the PMMA matrix. Such an approach consequently improves the mechanical properties, owing to enhanced dispersion as well as contributions from crack bridging. Finally, the use of emerging alternatives, such as nanoparticles, and the use of natural biomolecules were highlighted to improve bioactivity and antibacterial properties.

Chemical composition of cloud and rainwater at a high-altitude mountain site in western India: source apportionment and potential factors.

This study focuses on the chemical composition of cloud water (CW) and rainwater (RW) collected at Sinhagad, a high-altitude station (1450 m AMSL) located in the western region of India. The samples were collected during the monsoon over two years (2016-2017). The chemical analysis suggests that the concentration of total ionic constituents was three times higher in CW than in RW, except for NH4+ (1.0) and HCO3- (0.6). Compared to RW, high concentrations of SO42- and NO3- were observed in CW. The weighted average RW pH (6.5 ± 0.3) was slightly more alkaline than CW pH (6.1 ± 0.5). This can be attributed to the high concentrations of neutralizing ions such as nss-Ca2+, nss-Mg2+, K+, and NH4+, indicating the greater extent of wet scavenging during rainfall. These ions counteract the acidity generated by SO42- and NO3-. A high correlation between Ca2+, Na+, K+, NO3-, and SO42- makes it difficult to estimate the contribution of SO42- from different sources. Anthropogenic sulfur emissions and soil dust significantly influence the ionic composition of clouds and rain. Positive matrix factorization (PMF) was used to identify the contribution of different sources to the samples. In the CW, the extracted factors were cooking and vehicles, aging sea salt, agriculture, and dust. In RW, the factors were industries, cooking and vehicles, agriculture and dust, and aging sea salt. The findings of this study have significant implications for the monsoon build-up, ecosystems, agriculture, and climate change.

Bengali Migrant Workers in South India: A Mixed-Method Inquiry into Their Earnings, Livings and Struggle During Covid Pandemic.

This study has tried to compare the earning and non-earning aspects of migrant workers from West Bengal engaged in different types of work in Karnataka and Kerala based on survey of 111 Bengali-speaking migrant workers and a number of in-depth interviews and FGDs. The study has found that most of the migrant workers landed in south India only after working in Kolkata, northern or western Indian cities. Lack of regular employment opportunities and low-wage rate in rural as well as urban West Bengal are the dominant reasons for their migration. Hostile social environment and increasing earning uncertainties in northern and western Indian cities along with higher-wage rate in south India are reasons for the migrant workers shifting to south India. On an average, they earn Rs. 1.7 lakhs annually and are able to send almost two-thirds of their earnings as remittances. Except the rag pickers in Bengaluru, all other migrant workers live without their families at destination locations. The living conditions of the migrant workers, especially the rag pickers, are poor. Continuous inflow of migrant workers from eastern and north-eastern India is now a challenge for the incumbent Bengali migrant workers in south India; however, majority of them are not willing to return to West Bengal in future. The pandemic and successive rounds of lockdown in destination and home states have unsettled their lives. Not only their income has fallen, getting job and movement across different destination locations has become uncertain too. They have now hardly any resource to cope up with this continuing uncertainty.

Compensatory effect of biomass burning on black carbon concentrations during COVID-19 lockdown at a high-altitude station in SW India.

The characteristics of black carbon (BC) aerosols, their sources, and their impact on atmospheric radiative forcing were extensively studied during the COVID-19 lockdown (28th March-31st May 2020) at a high-altitude rural site over the Western Ghats in southwest India. BC concentration and the contribution of BC originating from biomass burning (BCbb) estimated from the aethalometer model during the lockdown period were compared with the same periods in 2017 and 2018 and with the pre-lockdown period (1st February to March 20, 2020). BC concentrations were 44, 19, and 17% lower during the lockdown period compared with the pre-lockdown periods of 2020 and similar periods (28th March to 31st May) of 2017 and 2018, respectively. BCbb contributed ∼50% to total BC during the lockdown period of 2020 and compensated for the decrease in BC concentration due to lower traffic emissions. The characteristics of light-absorbing organic carbon (brown carbon; BrC) absorption at 370 nm were evaluated during the lockdown and the pre-lockdown periods of 2020, 2017, and 2018. The BrC was estimated to be the highest during the lockdown period of 2020. Finally, atmospheric radiative forcing was calculated using the mean BC concentration during the pre-lockdown, lockdown, and similar periods (28th March to 31st May) of 2017 and 2018.

Social class related inequalities in household health expenditure and economic burden: evidence from Kerala, south India.

BACKGROUND: In the Indian context, a household's caste characteristics are most relevant for identifying its poverty and vulnerability status. Inadequate provision of public health care, the near-absence of health insurance and increasing dependence on the private health sector have impoverished the poor and the marginalised, especially the scheduled tribe population. This study examines caste-based inequalities in households' out-of-pocket health expenditure in the south Indian state of Kerala and provides evidence on the consequent financial burden inflicted upon households in different caste groups. METHODS: Using data from a 2003-2004 panel survey in Kottathara Panchayat that collected detailed information on health care consumption from 543 households, we analysed inequality in per capita out-of-pocket health expenditure across castes by considering households' health care needs and types of care utilised. We used multivariate regression to measure the caste-based inequality in health expenditure. To assess health expenditure burden, we analysed households incurring high health expenses and their sources of finance for meeting health expenses. RESULTS: The per capita health expenditures reported by four caste groups accord with their status in the caste hierarchy. This was confirmed by multivariate analysis after controlling for health care needs and influential confounders. Households with high health care needs are more disadvantaged in terms of spending on health care. Households with high health care needs are generally at higher risk of spending heavily on health care. Hospitalisation expenditure was found to have the most impoverishing impacts, especially on backward caste households. CONCLUSION: Caste-based inequality in household health expenditure reflects unequal access to quality health care by different caste groups. Households with high health care needs and chronic health care needs are most affected by this inequality. Households in the most marginalised castes and with high health care need require protection against impoverishing health expenditures. Special emphasis must be given to funding hospitalisation, as this expenditure puts households most at risk in terms of mobilising monetary resources. However, designing protection instruments requires deeper understanding of how the uncovered financial burden of out-patient and hospitalisation expenditure creates negative consequences and of the relative magnitude of this burden on households.

Effect of juice extraction methods and processing temperature-time on juice quality of Nagpur mandarin (Citrus reticulata Blanco) during storage.

Influence of juice extraction methods and pasteurization temperature and time on quality of mandarin (Citrus reticulata Blanco) juice was studied. The experiment consisted of 65 °C pasteurization temperature with 15, 25 and 35 min holding time; 75 °C with 10, 20 and 30 min and 85 °C with 5, 10 and 15 min holding times and two types of juice extraction methods. The experiment was laid out in factorial completely randomized Design with three replications. Juice extracted with screw type juice extractor and processed at 65 °C for 15 min maintained better qualitative characteristics like total soluble solids, acidity, ascorbic acid, sugars and non-enzymatic browning during 6 months storage. Naringin and limonin contents were minimum with the screw extractor and 65 °C processing temperature for 15 min.

Seasonal characteristics of boundary layer over a high-altitude rural site in Western India: implications on dispersal of particulate matter.

The temporal variability of the planetary boundary layer height (PBLH) over Mahabaleshwar was studied for a period of 1 year from 1 December 2015 to 30 November 2016 using microwave radiometer (MWR) observations. The PBLH over Mahabaleshwar was found to be the highest during the pre-monsoon (March-May) season and lowest during the winter (December-February) season. The seasonal mean of PBLH was estimated to be 339±88 m during winter, 485±70 m during pre-monsoon, 99±153 m during monsoon, and 438±24 m during post-monsoon season. Frequency distribution analysis of PBLH during pre-monsoon season revealed that the formation of turbulence internal boundary layer (TIBL) is evident. In contrast, cold and moist air mass during the monsoon season enhances the wind shear with lower buoyancy term which results in lowering of PBLH. The comparison of PBLH between MWR and radiosonde observations shows a good correlation (r2 = 0.66, p=0.001). The growth rate was observed to be 388 m/h during pre-monsoon, 206 m/h during winter, 57 m/h during monsoon, and 167 m/h during post-monsoon season. The seasonal mean concentration of PM2.5 was found to be 42.3±4.6 µg/m3during winter, 33.4±8.7 µg/m3 during pre-monsoon, 6.6±2.2 µg/m3 during monsoon, and 26.1±1.7 µg/m3during post-monsoon season. The effect of higher loading of scattering-type aerosol (dust particle) was also investigated as a case study. The analysis reveals the inverse relationship between the PBL height variability and the particulate loading indicating the importance of aerosol direct effect. Analysis of the ventilation coefficient (Vc) revealed that the dissipation potential was higher (1736 m2/s) during pre-monsoon season as compared to (1191 m2/s, 455m2/s, and 1580 m2/s) winter, monsoon, and post-monsoon seasons.

Enantioselective Synthesis of Tricyclic ß-Lactones by NHC-Catalyzed Desymmetrization of Cyclic 1,3-Diketones.

The NHC-catalyzed desymmetrization of cyclic-1,3-diketones allowing the enantioselective construction of tricyclic ß-lactones with five contiguous stereocenters, including two quaternary stereocenters, has been developed. The mild and operationally simple addition of α-bromoenals to cyclopentane-1,3-diketone derivatives proceeds via the initial formation of chiral α,ß-unsaturated acylazolium intermediates and culminates in a cascade reaction, following the Michael-aldol-lactonization pathway to deliver the ß-lactone derivatives in moderate to good yields and excellent selectivity.

Sub micron aerosol variability and its ageing process at a high altitude site in India: Impact of meteorological conditions.

The effect of relative humidity and temperature on the submicron aerosol variability and its ageing process was studied over a high altitude site, Mahabaleshwar in south-west India. The mass composition of non-refractory particulate matter of 1 µm (NR-PM1) size was obtained using Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM) along with the measurements on a few trace gases during winter (December 2017-February 2018) and summer season (20th March - 5th May 2018). Sulfate exhibited strong dependence on the relative humidity (RH) as its mass fraction increased with the increase in RH. The Sulfate oxidation ratio (SOR) calculated during summer season also showed an increasing trend with RH indicating the influence of aqueous phase oxidation on sulfate fraction. On the other hand, OOA showed remarkable enhancement in its mass fraction with the increase in temperature along with the corresponding increase in f44 and tropospheric ozone. OOA, ozone and f44 ratio increased 14-34%, 8-26% and 25-43% respectively with the increase in temperature from 18 to 30 °C. This is indicative of the dominance of photochemical ageing processes during high temperature conditions. The extent of photochemical ageing was found to be higher during summer season (mean temperature ∼25.4 ± 2.6 °C) as compared to winter season (mean temperature ∼20.5 ± 2.6 °C). The nitrate diurnal was majorly governed by gas to particle partitioning process during winter season, whereas the summertime nitrate diurnal was influenced primarily by its formation rate. The non parametric wind regression analysis revealed that the mass concentration during winter was majorly contributed by distant sources from north east direction while during summer the local sources were more dominant.