Combining simple amines with the bench-stable sulfinylamine Tr-NSO allows in situ preparation of reactive alkyl sulfinylamines, which when combined with alkyl radicals generated by photocatalytic decarboxylation, provides N-alkyl sulfinamides. The reactions are broad in scope and tolerate a wide variety of functional groups on both the acid and amine components. The sulfinamide products are used to prepare a selection of challenging S(VI) products. The method provides a convenient way to use reactive and unstable alkyl sulfinylamines.

Organophosphorus(V) fluorides have a long and tumultuous history, with early applications as toxins and nerve agents reflecting their poisonous past. Behind these very real safety considerations, there is also growing potential in a wide range of fields, from chemical biology to drug development. The recent inclusion of organophosphorus(V) fluorides in click chemistry exemplifies the promise these compounds possess and brings these molecules to the brink of a resurgence. In this Perspective, we delve into the history of P(V)-F compounds, discuss the precautions needed to work with them safely, and explore recent advancements in their synthesis and application. We conclude by discussing how this field can continue on a path toward innovation.

A modular synthesis of sulfondiimidoyl fluorides - the double aza-analogues of sulfonyl fluorides - allowing variation of the carbon and both nitrogen-substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, and N-fluorobenzenesulfonimide (NFSI), as the starting materials. The reactions are broad in scope, efficient, and scalable. We show that the sulfondiimidoyl fluoride products can be combined with amines to provide sulfondiimidamides, and with organolithium reagents to provide sulfondiimines, and that reactivity in these transformations can be modulated by variation of the N-substituents.

Quinoxaline molecule has gathered a great attention in medicinal chemistry due to its vide spectrum of biological activities and emerged as a versatile pharmacophore in drug discovery and development. Its structure comprises bicyclic ring of benzopyrazine and displays a range of pharmacological properties including antibacterial, antifungal, antiviral, anticancer and anti-inflammatory. This review summarizes the different strategies for the synthesis of quinoxalines and their anti-inflammatory properties acting through different mechanisms. Structure activity relationships have also been discussed in order to determine the effect of structural modifications on anti-inflammatory potential. These analyses illuminate critical structural features required for optimal activity, driving the design and synthesis of new quinoxaline analogues with better anti-inflammatory activities. The anti-inflammatory properties of quinoxalines are attributed to their inhibitory action on expression of several inflammatory modulators such as cyclooxygenase, cytokines, nuclear factor kappa-light-chain-enhancer of activated B cells (NFB) and p38 mitogen activated protein kinase (p38 MAPK). Activators of nuclear factor erythroid 2-related factor 2 (NRF2) and agonistic effect on opioid receptors have also been discussed. Hence, this review may provide a future template for the design and development of novel quinoxaline derivatives acting through different molecular targets as potential anti-inflammatory agents with better efficacy and safety profile.

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The 2,2-difluoroethyl group is an important lipophilic hydrogen bond donor in medicinal chemistry, but its incorporation into small molecules is often challenging. Herein, we demonstrate electrophilic 2,2-difluoroethylation of thiol, amine and alcohol nucleophiles with a hypervalent iodine reagent, (2,2-difluoro-ethyl)(aryl)iodonium triflate, via a proposed ligand coupling mechanism. This transformation offers a complementary strategy to existing 2,2-difluoroethylation methods and allows access to a wide range of 2,2-difluoroethylated nucleophiles, including the drugs Captopril, Normorphine and Mefloquine.

Dichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible-light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3-Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non-cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium-labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

We report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well as aromatic groups participate as migrating groups, yielding a variety of α,α-disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, and substituted arenes. The operationally simple and fully catalytic conditions prescribe 1 mol% benzothiazinoquinoxaline as organophotocatalyst, 0.5 mol% Co-salen, and 10 mol% lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. We showcase the utility of the protocol in late-stage drug diversifications.

Driven by escalating environmental concerns, synthetic chemistry faces an urgent need for a green revolution. Green chemistry, with its focus on low environmental impacting chemicals and minimized waste production, emerges as a powerful tool in addressing this challenge. Metrics such as the E-factor guide the design of environmentally friendly strategies for chemical processes by quantifying the waste generated in obtaining target products, thus enabling interventions to minimize it. Phthalocyanines (Pcs), versatile molecules with exceptional physical and chemical properties, hold immense potential for technological applications. This review aims to bridge the gap between green chemistry and phthalocyanine synthesis by collecting the main examples of environmentally sustainable syntheses documented in the literature. The calculation of the E-factor of a selection of them provides insights on how crucial it is to evaluate a synthetic process in its entirety. This approach allows for a better evaluation of the actual sustainability of the phthalocyanine synthetic process and indicates possible strategies to improve it.

Sulfinamidines are promising aza-SIV chiral building blocks in asymmetric synthesis and drug discovery. However, no report has documented their enantioselective synthesis. Here we present an enantioselective synthesis of sulfinamidines via electrophilic amination of sulfenamides using an enantiopure N-H oxaziridine. The resulting enantiomerically enriched primary sulfinamidines are configurationally stable at 90 oC in solution and show remarkable stability against organic acids and bases under non-aqueous conditions. We also demonstrate a one-pot, three-component, enantioselective synthesis of sulfinamides using N-H oxaziridine reagents.

Secondary battery as an efficient energy conversion device has been highly attractive for alleviating the energy crisis and environmental pollution. Hierarchical porous carbon (HPC) materials with multiple sizes pore channels are considered as promising materials for energy conversion and storage applications, due to their high specific surface area and excellent electrical conductivity. Although many reviews have reported on carbon materials for different fields, systematic summaries about HPC materials for lithium storage are still rare. In this review, we first summarize the main preparation methods of HPC materials, including hard template method, soft template method, and template-free method. The modification methods including porosity and morphology tuning, heteroatom doping, and multiphase composites are introduced systematically. Then, the recent advances in HPC materials on lithium storage are summarized. Finally, we outline the challenges and future perspectives for the application of HPC materials in lithium storage.