Self-assembly of a series carboxylic acid-functionalized naphthalene diimide (NDI) chromophores with varying number (n=1-4) methylene spacers between the NDI ring and acid group has been studied. The derivatives show pronounced aggregation due to synergistic effects H-bonding groups in syn-syn catemer motif π stacking chromophores. Solvent-dependent UV/Vis studies reveal existence monomeric dye molecules "good" solvent such as chloroform self-assembly "bad" solvents methylcyclohexane....

This study unravels the intricate kinetic and thermodynamic pathways involved in supramolecular copolymerization of two chiral dipolar naphthalene monoimide (NMI) building blocks (O-NMI S-NMI), differing merely by a single heteroatom (oxygen vs sulfur). O-NMI exhibits distinct polymerization features as compared to S-NMI terms its pathway complexity, hierarchical organization, chiroptical properties. Two self-assembly occur due interplay between competing interactions among NMI chromophores...

We disclose a transition-metal-free NaI/PPh3-mediated direct C-H alkylation of azauracils using N-(acyloxy)pthalimides (NHPIs) as readily available alkyl surrogates under visible light irradiation. Detailed mechanistic studies reveal formation photoactivated electron donor-acceptor (EDA) complex between NaI/PPh3, TMEDA, and NHPI ester establish the crucial role TMEDA in increasing activity photoredox system. The reaction demonstrates broad scope, scalability, appreciable functional group...

We conceptualized a novel disconnection approach for the synthesis of fused tetrahydroquinolines that exploits visible light-mediated radical (4 + 2) annulation between alkyl N-(acyloxy)phthalimides and N-substituted maleimides in presence DIPEA as an additive. The reaction proceeds through formation photoactivated electron donor-acceptor complex NHPI esters DIPEA, final were obtained complete regioselective fashion. methodology features broad scope good functional group tolerance operates...

We report a photoredox system comprising sodium iodide, triphenyl phosphine, and N,N,N',N'-tetramethylethylenediamine (TMEDA) that can form self-assembled tetrameric electron donor-acceptor (EDA) complex with diaryliodonium reagents (DAIRs) furnish aryl radicals upon visible light irradiation. This practical mode of activation DAIRs enables arylation an array heterocycles under mild conditions to provide the respective heteroaryl-(hetero)aryl assembly in moderate excellent yields. Detailed...

Increased demand for a carbon-neutral sustainable energy scheme augmented by climatic threats motivates the design and exploration of novel approaches that reserve intermittent solar in form chemical bonds molecules materials. In this context, inspired biological processes, artificial photosynthesis has garnered significant attention as promising solution to convert power into fuels from abundantly found H2O. Among two redox half-reactions photosynthesis, four-electron oxidation water...

Organosilicons are privileged skeletons in the domains of pharmaceutical chemistry, organic synthesis, and materials science. Hence, investigating catalytic techniques for synthesis organosilicon compounds has received a great deal emphasis. Carbosilylation alkenes is an efficient technique to introduce diverse molecular architectures containing silicon into chemical space. However, organohalides pseudohalides prerequisites most existing carbosilylation protocols. On other hand, utilization...

A mild and efficient organophotoredox-catalyzed redox-neutral cascade involving maleimides <italic>N</italic>-(acyloxy)phthalimides allowing the synthesis of otherwise inaccessible <italic>Z</italic>-selective alkoxy-alkylidenesuccinimides is achieved.

A divergent synthetic approach to access highly substituted indole scaffolds is illustrated. By virtue of a tunable electrochemical strategy, distinct control over the C-3 substitution pattern was achieved by employing two analogous 2-styrylaniline precursors. The chemoselectivity governed fine-tuning acidity amide proton, relying on appropriate selection N-protecting groups, and assisted reactivity electrogenerated intermediates. Detailed mechanistic investigations based cyclic voltametric...

Fixation and chemical reduction of CO2 are important for utilization this abundant resource, understanding the detailed mechanism C-O cleavage is needed rational development methods. Here, we describe a analysis reaction masked two-coordinate cobalt(i) complex, L tBuCo (where tBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO2, which yields two products cleavage, monocarbonyl complex tBuCo(CO) dicobalt(ii) carbonate (L tBuCo)2(μ-CO3). Kinetic studies...

An electrochemical method for the synthesis of unsymmetrically substituted NH-pyrroles is described. The synthetic strategy comprises a challenging heterocoupling between two structurally diverse enamines via sequential chemoselective oxidation, addition, and cyclization processes. A series aryl- alkyl-substituted were effectively cross-coupled from an equimolar mixture to synthesize various unsymmetrical pyrrole derivatives up 84 % yield. desired cross-coupling was achieved by tuning...

Solvents are crucial platforms in organic synthesis. Thereby, the choice of a solvent is critical order to develop sustainable eco-friendly synthetic methodologies. Hence, present consensus employ environmentally friendly solvents which have broad applications fine chemical syntheses, especially from context large-scale industrial preparations. In this review, we provide several examples for utilization 2-MeTHF, CPME, and 4-MeTHP reactions pertaining organometallic-, organo-, biocatalysis...

We report a sustainable and eco-friendly approach for selective N-alkylation of various amines by alcohols, catalyzed well-defined Zn(II)-catalyst, Zn(La)Cl2 (1a), bearing tridentate arylazo scaffold. A total 57 N-alkylated were prepared in good to excellent yields, out which 17 examples are new. The Zn(II)-catalyst shows wide functional group tolerance, is compatible with the synthesis dialkylated via double diamines, produces precursors high yields marketed drugs tripelennamine thonzonium...

An important objective in organic synthesis and medicinal chemistry is the capacity to access structurally varied complex molecules rapidly affordably from easily available starting materials. Herein, a protocol for divergent of benzofuran fused azocine derivatives spiro-cyclopentanone benzofurans has been developed via chiral bifunctional urea catalyzed reaction between aurone-derived α,β-unsaturated imine ynone followed by switchable annulation reactions Lewis base catalysts (DBU PPh3)...

Benzoperylenocarbazole (BPC), a unique carbazole-based organophotocatalyst, is reported herein as potent organo-photoreductant. Lower excited state oxidation potential (−2.0 V vs SCE) and reasonable lifetime (4.61 ns) render BPC an effective photosensitizer. Under irradiation of blue light employing low catalyst loading (0.5 mol %), plethora vicinal diols diamines were synthesized in excellent yields through reductive coupling carbonyls imines, respectively. Insight about the electronic...

Recycled plastic waste based self-immolative polyurethane has been synthesized and nanoformulated for tumor relevant pH induced charge modulation, efficient guest encapsulation triggered release in a controlled fashion.

Designing well-defined Zn-complexes for chemo-selective cross-coupling of primary and secondary alcohols overcoming the difficulties associated with activating Zn 2+ (d 10 )-metal species.

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations...

Abstract Catalytic hydrocupration of unsaturated carbon‐carbon bonds to generate organometallic nucleophiles has recently become an attractive alternative conventional stoichiometric reagents in the stereoselective synthesis. Herein, we have developed efficient and economical method synthesize enantiopure α ‐hydroxy allyl ketones via a copper hydride (CuH)‐catalyzed hydroacylation alkoxyallenes, significant advancement given scarcity reports on such scaffolds literature. DFT calculations...

Regioselective and enantioselective C−H functionalization is a valuable method for synthesizing chiral complex molecules. However, it often requires large amounts of toxic oxidants high temperature, making environmentally economically adverse. Additionally, these traditional approaches generally suffer from regioselectivity enantioselectivity issues. To overcome limitations, new mechanism needed to control both simultaneously. Herein, we report the first Pd catalyzed regioselective distal...

Regioselective and enantioselective C−H functionalization is a valuable method for synthesizing chiral complex molecules. However, it often requires large amounts of toxic oxidants high temperature, making environmentally economically adverse. Additionally, these traditional approaches generally suffer from regioselectivity enantioselectivity issues. To overcome limitations, new mechanism needed to control both simultaneously. Herein, we report the first Pd catalyzed regioselective distal...

Herein, we disclosed a copper-catalyzed carbogermylation of alkenes through 3,4-difunctionalization quinoxalin-2(1H)-one to afford 3-oxo-3,4-dihydroquinoxaline 1-oxide incorporated organogermanium derivatives. Despite extensive research on the C-H functionalization quinoxaline-2(1H)-one, difunctionalization this compound C-C and N-O bond formation via radical relay process is unusual. DFT calculation mechanistic studies reveal that reaction follows pathway.

Herein, we demonstrate chelating-group-assisted C(sp2)-O reductive elimination at gold(III) centers. Detailed stoichiometric studies highlighted the importance of a chelating group for achieving successful C-O elimination, paving way development catalytic version. The mechanistic investigations, including control experiments, 31P NMR, mass spectrometry, and density functional theory (DFT) studies, suggested that synergistic effect ligand creates highly coordinated environment around Au(III)...

The chameleon reductant: CO2 trapped by a frustrated Lewis pair is predicted to undergo BH activation mediated reduction NH3BH3, in contrast concerted NH3BH3 of free (see figure). This mechanism provides further fundamental understanding novel processes that could lead environmentally friendly and economically viable production renewable fuels. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

Abstract Multiple‐bonded iron‐oxo and ‐nitrido species have been identified or proposed as key intermediates in a range of important chemical transformations. The reported model complexes feature various coordination geometries distinct electronic structures, therefore exhibit diverse reactivity. present contribution highlights the synergy from both experimental theoretical standpoints to elucidate their different bonding situations delineate common mechanistic features hydrogen‐atom...