Controlling the oxidation of unactivated C(sp3)–H bonds through supramolecular catalyst–substrate interactions has recently enabled site-selective transformations previously considered inaccessible. However, progress has been hampered by lengthy linear syntheses of supramolecular catalysts. Here we present a convergent strategy that directly cross-couples preformed tetradentate aminopyridine ligands with recognition motifs, streamlining access to functional catalysts. Using this approach, we prepared four catalysts, two featuring resorcin[4]arene (RS) and two bearing calix[4]arene (CX) units, for substrate recognition using the solvophobic effect in 2,2,2-trifluoroethanol. This convergent synthesis reduces the longest linear sequence from 5 steps to 2 steps (starting from the recognition motif) by shifting from a linear, catalyst-specific synthesis to a modular platform that allows rapid assembly of catalyst libraries using premade, interchangeable building blocks.

Hydroxamic acidsand their derivatives are a versatileclass oforganic compounds with broad utility in synthetic chemistry. Thisreview highlights key synthetic transformations involving these molecules,covering important reactions such as their use in Weinreb amide chemistry,rearrangement processes, C–H activation directed by hydroxamategroups, their role as precursors to N-centered radicalsand aza-oxyallyl cations, reduction reactions, and umpolung transformationsinitiated by the N–O bond cleavage.

Phthalocyanine–gold nanoparticle (Pc–AuNP)conjugatescombine the unique properties of gold with the therapeutic potentialof phthalocyanines, offering a promising strategy for cancer therapy.Here, two novel carbazole-containing Pcs, axially disubstituted Si­(IV)and peripherally tetra-substituted Zn­(II) derivatives, were synthesizedand conjugated to gold nanoparticles of two core sizes (20 and 40nm). Characterization was performed using TEM and SEM techniques.Stability assays in complete medium showed a stronger aggregationtendency for SiPc–AuNPs than for ZnPc–AuNPs. Bright-fieldmicroscopy revealed that Pc–AuNPs induced detachment of A549lung adenocarcinoma cells but not HUVEC endothelial cells, highlightinga cell type–dependent effect. Despite this detachment, no significantloss of viability occurred at 72 h, underscoring the resilience ofA549 cells to membrane and cytoskeletal stress. Once internalized,both SiPc- and ZnPc-based nanoconjugates displayed similar cytoplasmicand perinuclear localization, suggesting uptake was dominated by theAuNP carrier. Preliminary MTT assays showed dye–particle interference,leading to use of the PrestoBlue assay, which avoids insoluble formazanartifacts. Viability analysis indicated that only Au40/SiPc transiently increased A549 reducing capacity at 24 h, likely dueto short-term ROS scavenging, which normalized by 72 h. Overall, thesefindings demonstrate how metal center, substitution geometry, andparticle size collectively affect aggregation, cellular interactions,and cytotoxic profiles, providing insights for optimizing Pc–AuNPsas nanophototherapeutic agents.

Late-stage catalytic oxidations of complex natural productshavebeen shown to exhibit dramatically improved chemoselectivity throughthe crucial use of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), evenin the presence of oxidatively sensitive groups, such as hydroxylsand diols. This strategy reduced the need for protecting groups, effectivelymimicking enzymatic pathways, and substantially enhancing syntheticideality in the preparation of ent-beyerane and ent-kaurane metabolites.

A practical and scalableprotocol for the deoxyfluorination ofhydroxyalkyl-substituted aryl- and alkenylboronates was developed.The optimized conditions (combining Deoxo-Fluor with TEA·3HFas the reagents and substrate preconversion to trifluoroborate salts)enabled efficient transformation across a wide range of (homo)­benzylicand allylic alcohols while tolerating protected carboxyl and aminogroups. The resulting fluorinated boronates performed well as versatilebuilding blocks in oxidation and Suzuki cross-coupling reactions.Furthermore, a telescoped one-pot strategy allowed direct utilizationof crude fluorinated intermediates, enabling access to complex molecularframeworks containing alcohol, carbonyl, and ester functionalities,typically intolerant to late-stage fluorination conditions. This methodologyoffers a general and efficient route for the incorporation of monofluorinatedaliphatic fragments into structures that are relevant for medicinalchemistry and materials science.

Selective functionalization of C­(sp3)–Hbondsremains challenging yet crucial for researchers. A frequently usedapproach by chemists to tackle this challenge involves leveraging1,2-metal migration/insertion, which enables the selective activationand cleavage of a specific C­(sp3)–H bond adjacentto or distant from the directing group. Palladium is among the mostcommonly employed catalysts for C­(sp3)–H functionalizationthrough metal migration/insertion, with Pd­(OAc)2 beingthe predominant palladium complex utilized in these processes. 1,2-Palladiummigration is a key strategy for achieving selective C­(sp3)–H functionalization. After palladium coordinates to a directinggroup, its migration can activate the nearby C­(sp3)–Hbond. With subsequent migrations, more distant C­(sp3)–Hbonds can be targeted and transformed into C­(sp3)–functionalgroups. During the 1,2-insertion of palladium, the migration of palladiumtakes place following the activation of the C­(sp3)–Hbond. This migration step typically involves the palladium insertinginto a double bond, which links the C­(sp3)–H bondto a C­(sp2)–H bond, thereby progressing the reaction.Ultimately, this review highlights that C­(sp3)–Hfunctionalization via 1,2-palladium migration/insertion has the potentialto selectively modify both proximal and remote C–H bonds inorganic molecules, offering a valuable tool for researchers to synthesizea wide range of organic compounds in future studies. This accountencompasses all types of 1,2-palladium migration/insertion and examinestheir impact on C­(sp3)–H functionalization. It providesa detailed analysis of the mechanisms involved and explores how thesemigrations enable the activation of both remote and proximal C­(sp3)–H bonds with the directing group.

A new methodfor the synthesis of cyclometalated gold­(III) complexesfeaturing (P^N^C) ligands is reported. This protocol employs a tandemoxidative addition/cycloauration process, enabling the formation of(P^N^C)­gold­(III)-aryl, -alkenyl and -alkynyl derivatives by creatingtwo Au–C bonds in one pot from a structurally diverse rangeof C­(sp2)- and C­(sp)-iodide substrates. Additionally, acomplementary two-step method was developed to access (P^N^C)­gold­(III)-alkynylcomplexes, which exhibit emission in the blue and green light regions.

Globally, breast cancer is the second leading cause ofcancer-relatedmortality among women. Early detection, accurate diagnosis, and timelytreatment are critical for improving survival rates. Therefore, developinga rapid and highly sensitive diagnostic method for early-stage breastcancer detection is essential. Human epidermal growth factor receptor2 (HER2) is a well-characterized indicator of aggressiveness and poorprognosis in various cancers, including breast cancer. HER2-positivebreast cancer represents about 15–20% of all cases, highlightingthe significance of HER2 as both a prognostic and predictive biomarker.Gold nanoparticles (AuNPs) have emerged as promising tools in cancerdiagnostics due to their unique optical and physicochemical properties.Among these, green-synthesized AuNPs are particularly attractive forbiomedical applications due to their eco-friendliness and biocompatibility. Andrographis paniculata is a medicinal herb traditionallyemployed in the treatment of several diseases. Its leaf extract (ALE)contains various bioactive compounds, including flavonoids and diterpenoids,known for their strong reducing capabilities suitable for AuNP synthesis.In this study, we synthesized AuNPs using ALE (ALE-AuNPs) througha green, one-pot method. The ALE-AuNPs ranged from 11.12 ± 2.10to 43.53 ± 10.53 nm in size, with a zeta potential of −21.00± 0.89 to −44.60 ± 2.36 mV. Cytotoxicity testingon MCF-7 cells indicated good biocompatibility. For targeted detection,the ALE-AuNPs were further functionalized with polyethylene glycol(PEG) and anti-HER2 antibodies, forming ALE-AuNPs+PEG+anti HER2. Thisnanoconjugate successfully detected HER2-positive MCF-7 cells viaa 3,3′,5,5′-tetramethylbenzidine-based colorimetricassay. To the best of our knowledge, this is the first report of asimple green synthesis of AuNPs from ALE for use as a colorimetricprobe in HER2-positive breast cancer detection.

Despite the frequent use of alcohols as solvents in GBB (Groebke-Blackburn-Bienaymé) protocols, the mechanistic reasons for their preference remain poorly understood. In this work, we combined experimental and theoretical investigations to elucidate the roles of solvents and reagents in the GBB reaction, revealing their noninnocent behavior. Kinetic experiments, high-resolution ESI-(+)-MS-(/MS), and DFT calculations demonstrated that methanol not only acts as a solvent but also as a cocatalyst, significantly influencing the reaction mechanism and accelerating key steps. We proposed both uncatalyzed and PTSA-catalyzed pathways, including alternative mechanisms involving solvent-participating intermediates. The reaction scope confirmed the method's robustness, and selected fluorescent products were successfully applied as bioimaging probes in live cells. These findings contribute to a deeper understanding of MCR mechanisms and highlight the critical impact of solvent and reagent effects on their efficiency.

Herein, we describe the photoredox activation of silanes under deep-red irradiation with or without osmium-based photocatalysts to generate silyl radicals. These radicals were further employed for achieving various reactivities previously unexplored in the red-light spectral region, such as hydrosilylation, hydrosulfonylation, and Giese reaction. Overall, the developed deep-red protocols allow for the preparation of a diverse array of high-value molecules.