Bipyridyl Functionalized NHC-Sulfenyl, Selenenyl Cations; Potential Species for Alkylation Reactions and Ligands in Copper(I) Catalysis.

Reactions of bipyridyl-functionalized imidazole-thiones and selones with MeX (X=I, OTf) afforded sulfenyl and selenenyl cations [(NNC)EMe]X (2/3, E=S, Se). Further reactions of these main-group cations with [Cu(CHCN)]BF, Cu(OTf) furnished dicationic [{Cu(μ-I)(NNC)EMe}][Y] (5/6, Y=BF, OTf) and tricationic copper(I) complexes [Cu{(NNC)EMe}](OTf)BF (7 a/7 b) when employed [(NNC)EMe]I and [(NNC)EMe]OTf respectively. All these cationic complexes were characterized by various spectroscopic techniques, including X-ray diffraction analysis.

Emerging Roles of Gossypol in Therapy: Innovations in Prodrug Design and Nanoformulation Frontiers.

Stimuli activatable systems have the potential to deliver drugs to targeted areas by releasing therapeutic agents in response to diseased specific microenvironments such as the acidic environment commonly found in diseased tissues. This review article focuses on gossypol, a bioactive compound with inherent toxicity attributed to various factors, including the presence of its formyl groups. It highlights the potential of imine-linked gossypol-based prodrugs and nanoparticle formulations for targeted delivery and controlled release.

Synthesis of Spirocyclic-1,3-Indandione Containing-Cyclopentenones and -Benzotropones.

Synthesis of functionalized 1,3-indandiones containing-cyclopentenones and -benzotropones has been achieved by the reaction of 1,5-diphenylpenta-1,4-diyn-3-ones with 1,3-indandiones, bindone respectively. The developed method involves Michael-anti-Michael addition cascade reactions under transition-metal-free conditions. This is the first report to synthesise diverse benzotropone fused with 1,3-indandiones under transition metal-free conditions from bindone.

NHC Ligand-Enabled Cu(I)-Catalyzed Double Hydroamination: A Regio- and Chemoselective Bicyclization of -Amino 1,6-Diyne.

In this work, we have developed an efficient method for the intramolecular double hydroamination of aniline by employing -amino 1,6-diyne as a potential starting material. This protocol enables easy access to bioactive motif 3,4-dihydro-1-[1,4]oxazino[4,3-]indole through an intramolecular cascade bicyclization and concomitant isomerization pathway in one pot. This transformation has been effectively achieved by utilizing a stereoelectronically tuned, π-accepting NHC-supported copper(I) system.

A Three-Component Synthesis of Spiropyrrolines.

A rapid synthesis of medicinally important spiropyrrolines has been achieved by the reaction of 1,3-indanediones, benzaldehyde, and (1-azidovinyl)benzene under catalyst- and reagent-free conditions. This is the first report to synthesize diverse spiropyrroline compounds from readily available feedstock materials under metal-free conditions.

Total Synthesis and Determination of the Absolute Configuration of Berkeleylactone I.

Herein, we report the first total synthesis of berkeleylactone I and its 12 diastereomer. Consequently, this chemical synthesis allowed us to establish the unknown absolute stereochemistry at the C-12 center as 12, which was unidentified by the isolation group. This synthetic approach includes several critical reactions, such as the Sharpless asymmetric dihydroxylation, Baran's Ni-catalyzed alkyl-alkyl cross-coupling reaction, Brown allylation, Mitsunobu reaction, and ring-closing metathesis, as key steps.

Plants and global warming: challenges and strategies for a warming world.

In this review, we made an attempt to create a holistic picture of plant response to a rising temperature environment and its impact by covering all aspects from temperature perception to thermotolerance. This comprehensive account describing the molecular mechanisms orchestrating these responses and potential mitigation strategies will be helpful for understanding the impact of global warming on plant life. Organisms need to constantly recalibrate development and physiology in response to changes in their environment.

Synthetically Tunable Suprahybrid Nanoparticle Platform for the Efficacious Delivery of Therapeutics.

The discovery of lipid-hybrid nanosystems has offered potential solutions to various drug delivery and theranostic challenges. However, in many instances, the commonly used lipids and other components in these systems often pose challenges related to their solubility, physicochemical properties, immune compatibility, and limited synthetic tunability. In this work, we introduce a synthetically tunable supramolecular scaffold with amphiphilic characteristics based on the calix[4]arene macrocyclic system.

Synthesis of Highly Functionalized Spirocycles and Pentafulvene-Containing Dyes Involving 2-(2'-ketoalkyl)-1,3-indandiones.

Synthesis of highly functionalized spiro[4.4]nonane and spiro[4.5]decane motifs by the reaction of dimethylacetylenedicarboxylate (DMAD) with 2-(2'-ketoalkyl)-1,3-indandiones and 2-(3'-ketoalkyl)-1,3-indandiones, respectively, has been developed by utilizing a catalytic amount of DABCO.

New cationic coinage metal complexes featuring silyl group functionalized phosphine: syntheses, structures and catalytic studies in alkyne-azide cycloaddition reactions.

A series of coinage metal complexes bearing rarely explored -silylated phosphine is reported. The treatment of diphenyl(2-(trimethylsilyl)phenyl)phosphine (1) with CuCl and [Cu(CHCN)]BF furnished the corresponding neutral [(1)CuCl] (2) and mono-cationic [(1)Cu(CHCN)]BF (3) complexes, respectively. The reactions of 1 with AgX (X = BF, NO) in 2 : 1 ratio furnished the corresponding mono cationic dicoordinate silver(I) complexes of the type [(1)Ag]X (X = BF (4a), NO (4b)).

Dicationic copper(I) complexes bearing ENE (E = S, Se) pincer ligands; catalytic applications in regioselective cyclization of 1,6-diynes.

Two novel dicationic binuclear Cu(I) complexes of the type [{(BPPP)E}Cu][BF] (E = S (3a); Se (3b)) bearing (BPPP)E (BPPP = bis(diphenylphosphino)pyridine) pincer systems were isolated, and structurally characterized. The solid-state structures of 3a/3b display the presence of intermolecular cuprophilic (Cu⋯Cu) interactions between the two monocationic species, and consist of weak Cu⋯S bonding between the two cations. Besides, complex 3a was introduced as a molecular copper(I) catalyst in cyclization reactions, and new protocols were developed for the synthesis of a series of new oxazole and triazole derivatives bearing alkyne-phenyl propargylic ether substituents.

Cascade Nucleophilic Addition-Cyclic Michael Addition of Arynes and Indoles Bearing Michael Acceptor: A Strategy to Construct Pyrroloacridines and Study of Their Physicochemical Properties.

A facile synthetic approach to 6-pyrrolo[3,2,1-]acridines has been developed by using cascade -nucleophilic addition-cyclic Michael addition process of arynes and indoles substituted with Michael acceptors under metal-free conditions. Additionally, photophysical studies of a few of the newly synthesized pyrroloacridine compounds indicated good fluorescence emission properties.

A Method to Access Highly Functionalized Dibenzobicyclo[3.2.1]octadienones: Application to the Construction of the 6/6/5/6/6 Carbon Skeleton of Rubialatin A.

The dibenzobicyclo[3.2.1]octadienone scaffold, which has been found in naphthocyclinones, engelharquinones, rubialatin A, etc.

Total synthesis of proposed elgonene C and its (4,5)-diastereomer.

The total synthesis of the proposed elgonene C (1) and its (4,5)-diastereomer (1a) has been achieved using a second-generation oxazaborolidinium ion-catalysed Diels-Alder reaction, Sharpless asymmetric dihydroxylation, and a Ni-catalysed cross-carboxyl coupling reaction redox-active ester (RAE) formation as key reactions. The spectral and analytical data for our synthetic compounds 1 and 1a do not match the isolation data provided by Stadler . which indicates that structural revision is required for the proposed elgonene C.

N-Heterocyclic Carbene Analogues of Nucleophilic Phosphinidene Transition Metal Complexes.

Chloride abstraction from the complexes [(η -p-cymene){(IDipp)P}MCl] (2 a, M=Ru; 2 b, M=Os) and [(η -C Me ){(IDipp)P}IrCl] (3 b, IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr ) in the presence of trimethylphosphine (PMe ), 1,3,4,5-tetramethylimidazolin-2-ylidene ( IMe) or carbon monoxide (CO) afforded the complexes [(η -p-cymene){(IDipp)P}M(PMe )]BAr ] (4 a, M=Ru; 4 b, M=Os), [(η -p-cymene){(IDipp)P}Os( IMe)]BAr ] (5) and [(η -C Me ){(IDipp)P}IrL][BAr ] (6, L=PMe ; 7, L= IMe; 8, L=CO). These cationic N-heterocyclic carbene-phosphinidene complexes feature very similar structural and spectroscopic properties as prototypic nucleophilic arylphosphinidene complexes such as low-field P NMR resonances and short metal-phosphorus double bonds. Density functional theory (DFT) calculations reveal that the metal-phosphorus bond can be described in terms of an interaction between a triplet [(IDipp)P] cation and a triplet metal complex fragment ligand with highly covalent σ- and π-contributions.

Strategies for the construction of γ-spirocyclic butenolides in natural product synthesis.

Over the last four decades, a number of γ-spirocyclic butenolide containing natural products, drugs, and medicinally useful synthetic compounds have been reported. In this review, we discuss diverse chemical approaches to synthesize γ-spiro butenolides and their application towards natural product synthesis. The collective perception of various methods may allow superior approaches capable of delivering efficient synthetic approaches to obtain γ-spiro butenolide comprising natural products and their hybrid analogues for further drug discovery and development.

Anion Sensing by Novel Triarylboranes Containing Boraanthracene: DFT Functional Assessment, Selective Interactions, and Mechanism Demonstration.

Analytical methods often involve expensive instrumentation and tedious sample pretreatment for an analyte detection. Being toxic and detrimental to human health, sensing of cyanide (CN), fluoride (F), chloride (Cl), bromide (Br), nitrate (NO ), acetate (CHCOO), and bisulfate (HSO ) is performed by a boron-based molecular receptor, ,,,3,5-pentamethyl-4-{2-thia-9-boratricyclo[8.4.

Isolation of Carbene-Stabilized Arsenic Monophosphide [AsP] and its Radical Cation [AsP] and Dication [AsP].

Arsenic monophosphide (AsP) species supported by two different N-heterocyclic carbenes were prepared by reaction of (IDipp)PSiMe (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with (IMes)AsCl (2) (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) to afford the dichloride [(IMes)As(Cl)P(IDipp)]Cl (3), which upon reduction with KC furnished heteroleptic [(IMes)AsP(IDipp)] (4). The corresponding mono- and dications [(IMes)AsP(IDipp)][PF ], [5]PF , and [(IMes)AsP(IDipp)][GaCl ] [6][GaCl ] , respectively, were prepared by one-electron oxidation of 4 with ferrocenium hexafluorophosphate, [Fc]PF or by chloride abstraction from 3 with two equivalents of GaCl , respectively. Compounds 4-6 represent rare examples of heterodiatiomic interpnictogen compounds, and X-ray crystal structure determinations together with density functional theory (DFT) calculations reveal a consecutive shortening of the As-P bond lengths and increasing bond order, in agreement with the presence of an arsenic-phosphorus single bond in 4 and a double bond in 6 .