Visible-Light Driven Synthesis of Vinyl Amines without Photocatalyst.

We developed a visible-light-induced vinyl amination of activated alkenes using TMSN3 and CsF through EDA complex formation under an oxygen atmosphere. Without light, the EDA complex forms between activated alkene, CsF, and oxygen. Upon exposure to light, oxygen in the complex gets excited, initiating the HAT process. This method efficiently synthesizes vinyl-amine derivatives via a radical pathway, demonstrating good functional group tolerance and high yields in a short time. Further, the late-stage functionalization enables the synthesis of biologically active heterocycles.

An organo-photocatalyzed visible-light-driven multi-component approach for carbothioaryl/alkylation of activated alkenes via C(sp3)-H bond functionalization.

A visible-light-driven organophotocatalyzed multi-component approach for carbothiolation of activated alkenes is demonstrated under environmentally benign and redox-neutral conditions, involving direct C(sp3)-H functionalization followed by electrophilic alkyl/arylthiolation. The three-component difunctionalization reaction is a complete transition-metal and peroxide-free process conducted under milder conditions. In this composite reaction, by employing bench-stable reagents, the formation of two new C(sp3)-C(sp3) and C(sp3)-S bonds is achieved for a wide variety of substrates, showcasing the excellent functional group tolerance and chemoselectivity of the methodology. Furthermore, the scalability and utilization of natural sunlight instead of artificial blue LEDs, along with the use of an inexpensive and easy-to-prepare pyrylium salt as an organo-photocatalyst, make this protocol greener and more energy efficient.

Visible-Light-Driven Organophotocatalyzed Multicomponent Approach for Tandem C(sp3)-H Activation and Alkylation Followed by Trifluoromethylthiolation.

A visible-light-driven organophotocatalyzed multicomponent approach has been developed for tandem direct C(sp3)-H activation and alkylation followed by trifluoromethylthiolation in a one-pot operation. We report a completely metal-free, tandem, three-component approach for the difunctionalization of activated alkenes via the photoinduced radical pathway. This protocol allows the formation of two new C(sp3)-C(sp3) and C(sp3)-SCF3 bonds using a bench-stable, easy-to-handle trifluoromethylthiolating reagent under mild reaction conditions. The generosity of this reaction is shown with a library of C(sp3)-H donors and alkenes derivatives. The reaction conditions can tolerate a wide variety of functional groups. Gram-scale synthesis using environmentally benign and straightforward conditions highlights the synthetic advancement of the methodology. Further functionalization of the final product is also successfully demonstrated.

Visible-Light-Driven Organophotocatalyzed Mono-, Di-, and Tri-C(sp3)-H Alkylation of Phosphoramides.

A photocatalytic metal-free, visible-light-driven, highly atom-economic, direct multiple α-C(sp3)-H alkylation of phosphoramides and thiophosphoramides is demonstrated under environmentally benign conditions. Economically viable and commercially available Eosin-Y is used as an HAT photocatalyst for mono-α-C(sp3)-H alkylation of phosphoramide derivatives. Remarkably, di- and tri-C(sp3)-H alkylation of phosphoramides and thiophosphoramides using an acridinium photocatalyst is reported with good yield and selectivity. Mechanistic studies reveal that monoalkylation of phosphoramides by Eosin-Y follows the HAT mechanism, whereas di- and tri-C(sp3)-H alkylation by the acridinium photocatalyst follows the SET mechanism.

Ammonium Chloride-Mediated Trifluoromethylthiolation of p-Quinone Methides.

Ammonium chloride-mediated trifluoromethylthiolation of p-quinone methides is reported using inexpensive and bench stable AgSCF3 as a nucleophilic trifluoromethylthiolating (-SCF3) reagent. This method is an efficient strategy for the construction of the benzylic C(sp3)-SCF3 bond to synthesize trifluoromethylthio-diarylmethane derivatives by 1,6-conjugate addition/aromatization under mild reaction conditions without any metal catalyst, oxidants, or additives. This is the first report of trifluoromethylthiolation of p-quinone methides. In addition, di-trifluoromethylthiolation of δ-chloro-p-quinone methide and scalability are demonstrated.

Short-term exposure to ambient air quality of the most polluted Indian cities due to lockdown amid SARS-CoV-2.

Air pollution has happened to be one of the mounting alarms to be concerned with in many Indian cities. COVID-19 epidemic endow with a unique opportunity to report the degree of air quality improvement due to the nationwide lockdown in 10 most polluted cities across the country. National Air Quality Index (NAQI) based on continuous monitoring records of seven criteria pollutants (i.e. common air pollutants with known health impacts e.g. PM10, PM2.5, CO, NO2, SO2, NH3 and O3) for a total of 59 stations across the cities, satellite image derived Aerosol Optical Depth (AOD) and few statistical tools are employed to derive the outcomes. NAQI results convey that 8 cities out of the 10 air quality restored to good to satisfactory category during the lockdown period. Within week+1 of the lockdown period, PM10 and PM2.5 concentrations have suppressed below the permissible limit in all cities. CO and NO2 have reduced to about -30% and -57% respectively during the lockdown period. Diurnal concentrations of PM10 and PM2.5 have dropped drastically on the very 4th day of lockdown and become consistent with minor hourly vacillation. In April 2020 the AOD amount was reduced to about 36% and 18% in contrast to April 2018 and April 2019 respectively. This add-on reporting of the possible recovery extent in air quality may help to guide alternative policy intervention in form of short term lockdown so as to testify whether this type of unconventional policy decisions may be put forward to attain a green environment. Because, despite numerous restoration plans, air pollution levels have risen unabated in these cities. However, detailed inventory needs to be focused on identifying the localized pollution hotspots (i.e. source contribution).

Metal-Free Visible-Light-Promoted Trifluoromethylation of Vinylcyclopropanes Using Pyrylium Salt as a Photoredox Catalyst.

Visible-light-induced metal-free trifluoromethylation of activated, carbocyclic, and unactivated vinylcyclopropanes via a ring-opening reaction using the Langlois reagent (CF3SO2Na) is reported to synthesize allylic trifluoromethylated derivatives. Allylic trifluoromethylation was achieved by a photo-oxidative single electron transfer (SET) process at an ambient temperature and under metal-free conditions and visible-light irradiation using pyrylium salt as a photoredox catalyst. The reported methodology has an operational simplicity, broad substrate scope, high functional group tolerance, and scalability.

Metal-Free Photoredox Four-Component Strategy to 1,3-Functionalized BCP Derivatives.

Trifluoromethyl bicyclo[1.1.1]pentanes (BCPs) have attracted significant attention from the scientific community and pharmaceutical industries due to their advantageous physicochemical properties as arene bioisosteres. Initial photoredox perfluoroalkylation of [1.1.1]propellane triggers the tandem reaction to the perfluoroalkyl BCP radical followed by Giese addition to an in situ generated electron-deficient alkene by Knoevenagel condensation in a four-component fashion to form 1,3-functionalized BCPs. This strategy provides easy access to various 1,3-functionalized perfluoroalkyl BCP derivatives with the added advantage of nitrile group as a functional handle to diversified transformations. This methodology offers scalability and late-stage derivatization of drug molecules with high chemoselectivity.

Diastereoselective palladium-catalyzed C(sp3)-H cyanomethylation of amino acid and carboxylic acid derivatives.

In this study, we report an efficient protocol for Pd-catalyzed methylene ß-C(sp3)-H cyanomethylation of 8-aminoquinoline-directed α-amino acids using inexpensive chloroacetonitrile. Iodoacetonitrile generated in situ from chloroacetonitrile reacts with methylene C(sp3)-H bonds of α-amino acids with excellent diastereoselectivity, enabling access to a wide range of important γ-cyano-α-amino acids. Our protocol works well with different amino acid and carboxylic acid derivatives with good chemical yields and high functional group tolerance.

TEMPO-Mediated Selective Synthesis of Isoxazolines, 5-Hydroxy-2-isoxazolines, and Isoxazoles via Aliphatic δ-C(sp3)-H Bond Oxidation of Oximes.

Selective synthesis of three different bioactive heterocycles; isoxazolines, 5-hydroxy-2-isoxazolines and isoxazoles from the same starting material using TEMPO (2,2,6,6-Tetramethylpiperidin-1-oxyl) as a radical initiator is reported. Selectivity was achieved using different oxidants with TEMPO. The reaction goes through a 1,5-HAT (hydrogen atom transfer) process resulting in products with good yields. This strategy offers a straightforward route to three different heterocycles from oximes via radical-mediated C(sp3 )-H oxidation.

Some respite for India's dirtiest river? Examining the Yamuna's water quality at Delhi during the COVID-19 lockdown period.

The Yamuna's stretch within Delhi is considered as the dirtiest river reach in India and despite numerous restoration plans, pollution levels have risen unabated. However, the enforcement of a nationwide lockdown due to the ongoing COVID-19 pandemic can possibly provide a ray of hope. We analyze the lockdown's impact on the water quality status of this stretch using a combination of measured parameters and satellite image derived indices. Class C Water Quality Index estimates of nine stations indicate an improvement of 37% during the lockdown period. The Biological Oxygen Demand and Chemical Oxygen Demand values reduced by 42.83% and 39.25%, respectively, compared to the pre-lockdown phase, while Faecal Coliform declined by over 40%. Similar analysis of 20 major drains that meet the Yamuna revealed declining effluent loads and discernable improvements in drain contaminant status were ascertained via a hierarchical cluster analysis. Reach-wise suspended particulate matter content, turbidity and algal signatures were derived from multi-temporal Landsat-8 images of prior and ongoing lockdown periods for 117 channel segment zones. These parameters also declined notably within most stretches, although their extents were spatially varied. While the partial/non-operational status of most industries during the lockdown enabled significant reduction in effluent loads and a consequent betterment in the river water quality, its spatial variations and even deterioration in some locations resulted from the largely undiminished inflow of domestic sewage through multiple drains. This study provides an estimate of possible river recovery extents and degree of improvement if deleterious polluting activities and contaminants are regulated properly.

Effect of lockdown amid COVID-19 pandemic on air quality of the megacity Delhi, India.

Amid the COVID-19 pandemic, a nationwide lockdown is imposed in India initially for three weeks from 24th March to 14th April 2020 and extended up to 3rd May 2020. Due to the forced restrictions, pollution level in cities across the country drastically slowed down just within few days which magnetize discussions regarding lockdown to be the effectual alternative measures to be implemented for controlling air pollution. The present article eventually worked on this direction to look upon the air quality scenario amidst the lockdown period scientifically with special reference to the megacity Delhi. With the aid of air quality data of seven pollutant parameters (PM10, PM2.5, SO2, NO2, CO, O3 and NH3) for 34 monitoring stations spread over the megacity we have employed National Air Quality Index (NAQI) to show the spatial pattern of air quality in pre and during-lockdown phases. The results demonstrated that during lockdown air quality is significantly improved. Among the selected pollutants, concentrations of PM10 and PM2.5 have witnessed maximum reduction (>50%) in compare to the pre-lockdown phase. In compare to the last year (i.e. 2019) during the said time period the reduction of PM10 and PM2.5 is as high as about 60% and 39% respectively. Among other pollutants, NO2 (-52.68%) and CO (-30.35%) level have also reduced during-lockdown phase. About 40% to 50% improvement in air quality is identified just after four days of commencing lockdown. About 54%, 49%, 43%, 37% and 31% reduction in NAQI have been observed in Central, Eastern, Southern, Western and Northern parts of the megacity. Overall, the study is thought to be a useful supplement to the regulatory bodies since it showed the pollution source control can attenuate the air quality. Temporary such source control in a suitable time interval may heal the environment.