Isatoic anhydride as a masked directing group and internal oxidant for Rh(III)-catalyzed decarbonylative annulation through C-H activation: insights from DFT calculations.

Density functional theory calculations uncovered a new mechanism for the rhodium-catalyzed decarbonylative annulation of isatoic anhydride with alkynes, in which the acyloxy group formed from the N-H deprotonation and C-O bond cleavage of isatoic anhydride acts as the directing group to assist the C-H activation. From the generated five-membered rhodacycle intermediate, the final aminoisocoumarin product could be formed by subsequent steps of alkyne insertion, reductive elimination, decarbonylation, and protonation. The isocyanate moiety contained in the annulation intermediate was uncovered as a novel internal oxidant for the reaction, which oxidizes the Rh(I) to Rh(III) by decarbonylation.

Probing Deuteration-Induced Phase Separation in Supported Lipid Monolayers using Hyperspectral TERS Imaging.

In this study, we investigate the impact of deuteration on the formation of phase-separated domains in supported lipid monolayers using hyperspectral Tip-Enhanced Raman Spectroscopy (TERS) imaging. The intricate organization of biological membranes plays a crucial role in cellular functions. Various factors that influence domain formation have been identified in previous studies such as lipid tail length and cholesterol concentration.

Expression of concern: Direct C-S bond formation C-O bond activation of phenols in a crossover Pd/Cu dual-metal catalysis system.

Expression of concern for 'Direct C-S bond formation C-O bond activation of phenols in a crossover Pd/Cu dual-metal catalysis system' by Vahid Khakyzadeh , , 2019, , 4491-4497, https://doi.org/10.1039/C9OB00313D.

Selectivity in the Formal [2 + 2 + 2] Cycloaromatization of Enyne-Allenes Generated by the Alder-ene Reaction from Triynes.

1,3-Diynyl propiolates undergo the Alder-ene reaction to generate enyne-allenes, which participate in the Diels-Alder reaction to provide products of a formal [2 + 2 + 2] cycloaromatization of three alkynes. Without an external alkyne, enyne-allene reacts with one of the alkyne moieties of 1,3-diynyl propiolate, whereas external alkynes can be used to trap enyne-allene to provide various arene products. The substituents on the dienophilic alkynes have a profound impact on their reactivity.

Does arginine aggregate formation in aqueous solutions follow a two-step mechanism?

The formation of aggregates was studied in arginine aqueous solutions using light scattering. The main driving force for aggregate formation is hydrogen bonding between the arginine (Arg) amino acids, which is partially verified using density functional theory calculations. The measurement of energy loss during this process, coupled with Cryo-EM morphology data, indicates that these aggregates are in the solid state.

Ligand-Controlled Cobalt-Catalyzed Regiodivergent and Stereoselective Ring-Opening Isomerization of Vinyl Cyclopropanes.

A ligand-controlled regiodivergent and stereoselective ring-opening isomerization of vinylcyclopropane was developed with cobalt catalysis. Employing the commercially available Xantphos ligand, the reactions afforded exclusively linear-type 1,3-dienes as the products. Interestingly, when switching the ligand to an amido-diphosphine ligand (PNP), branched-type 1,3-dienes were obtained with high regioselectivity and stereoselectivity.

Cyclization Reactions of In Situ-Generated Acyl Ketene with Ynones to Form Oxacycles.

Acyl ketenes react with polar unsaturated functional groups to give unique heterocyclic rings, yet reactions with unpolarized unsaturated functional groups have not been reported. Herein, we describe two effective ring-forming reactions between acetyl ketene and electron-deficient alkynes. The first reaction involves in situ tethering between acetyl ketene and nucleophile-containing 1,3-diynones, which promotes sequential intramolecular 1,6/1,4-additions to generate 2-methylene-2-pyrans in various yields (24-91%).

Photoredox-Catalyzed Hydroacylation of Azobenzenes with Carboxylic Acids.

Acyl hydrazides are widely found in bioactive compounds and have important applications as versatile synthetic intermediates. In the current report, a photoredox-catalyzed hydroacylation of azobenzenes was disclosed with carboxylic acids as the acylation reagent, affording a variety of -disubstituted hydrazides. The process possesses the advantages of mild reaction conditions, broad substrate scope, and high efficiency.

A General Protocol toward Synthesis of 3-Methylindoles Using Acenaphthoimidazolyidene-Ligated Oxazoline Palladacycle.

An efficient catalytic strategy toward the synthesis of -substituted 3-methylindoles from inactive -dihaloarenes and -allylamines was developed by using a 1,3-bis(2,6-diisopropylphenyl)acenaphthoimidazol-2-ylidene (AnIPr)-ligated oxazoline palladacycle. It enabled a very broad substrate scope tolerating different functional groups, electronic properties, and steric bulkiness and afforded desired products in good to excellent yields. Importantly, it showed great potential to synthesize several bioactive compounds and key intermediates of natural products in high yields.

Study on the Dynamic Changes in Non-Volatile Metabolites of Rizhao Green Tea Based on Metabolomics.

The processing of tea leaves plays a crucial role in the formation of the taste of the resulting tea. In order to study the compositions of and changes in taste-related substances during the processing of Rizhao green tea, non-targeted metabolomics was used, based on UHPLC-Q Exactive MS. Totals of 529, 349, and 206 non-volatile metabolites were identified using three different detection modes, of which 112 secondary metabolites were significantly changed.

Condition-Controlled -Acylation and N-O Bond Reduction of Hydroximic Acids with Thioacetic Acid.

Condition-dependent transformations between hydroximic acids and thioacetic acid were achieved. Using NHHCO in the ethanol solvent, efficient N-O bond cleavage of hydroxamic acids occurred to afford primary amides with high functional group compatibility. The reaction was switched to -acylation when NEt and HO were used as the base and solvent, respectively.

Cobalt-Catalyzed Asymmetric Hydrosilylation of α-Oxygenated Ketones.

An asymmetric hydrosilylation of α-oxygenated ketones was developed under the catalysis of Co(OAc) in combination with a chiral phosphine-amido-oxazoline (PAO) ligand, providing a mild, efficient, and enantioselective access to a variety of synthetically useful 1,2-diol derivatives. This protocol can be carried out at the gram scale with a catalyst loading of 1 mol %, and its synthetic utility was demonstrated by efficient conversion of the optically enriched products into chiral α-hydroxy acid, 1,3-dioxolan-2-one, ethylene oxide, and 1,2,3-1-triazole.

Visible-Light-Promoted Hydrogenation of Azobenzenes to Hydrazobenzenes with Thioacetic Acid as the Reductant.

A catalyst- and metal-free hydrogenation of azobenzenes to hydrazobenzenes in the presence of thioacetic acid was achieved under visible light irradiation. The transformation was carried out under mild conditions in an air atmosphere at ambient temperature, generating a variety of hydrazobenzenes with yields up to 99%. The current process is compatible with a variety of substituents and is highly chemoselective for azo reduction when other unsaturated functionalities (carbonyl, alkenyl, alkynyl, etc.

Cycloisomerization of Alkyne-Tethered N-Acyloxycarbamates to 2-(3H)Oxazolones through Nitrenoid-Mediated Carboxyamidation.

The cycloisomerization of alkyne-tethered N-benzoyloxycarbamates to 2-(3H)oxazolones is described. Two catalytic systems are tailored for intramolecular 5-exo-alkyne carboxyamidation and concomitant alkene isomerization. PtCl /CO (5 mol%, toluene, 100 °C) promotes both carboxyamidation and alkene isomerization but has a limited substrate scope.

Defect-engineered surfaces to investigate the formation of self-assembled molecular networks.

Herein we report the impact of covalent modification (grafting), inducing lateral nanoconfinement conditions, on the self-assembly of a quinonoid zwitterion derivative into self-assembled molecular networks at the liquid/solid interface. At low concentrations where the compound does not show self-assembly behaviour on bare highly oriented pyrolytic graphite (HOPG), close-packed self-assembled structures are visualized by scanning tunneling microscopy on covalently modified HOPG. The size of the self-assembled domains decreases with increasing the density of grafted molecules, the molecules covalently bound to the surface.

Covalent transfer of chemical gradients onto a graphenic surface with 2D and 3D control.

Control over the functionalization of graphenic materials is key to enable their full application in electronic and optical technologies. Covalent functionalization strategies have been proposed as an approach to tailor the interfaces' structure and properties. However, to date, none of the proposed methods allow for a covalent functionalization with control over the grafting density, layer thickness and/or morphology, which are key aspects for fine-tuning the processability and performance of graphenic materials.

Iron(II)-Catalyzed Nitrene Transfer Reaction of Sulfoxides with -Acyloxyamides.

An iron(II)-catalyzed nitrene transfer reaction of sulfoxides with -acyloxyamides has been developed, leading to the efficient construction of acyl sulfoximines with high functional-group compatibility. The current catalytic transformation was carried out under an air atmosphere at ambient temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. Application of the methodology was demonstrated by facile C-H acetoxylation and olefination using the acyl sulfoximine as the directing group.

Development of an Allenyne-Alkyne [4+2] Cycloaddition and its Application to Total Synthesis of Selaginpulvilin A.

A new [4+2] cycloaddition of allenyne-alkyne is developed. The reaction is believed to proceed with forming an α,3-dehydrotoluene intermediate. This species behaves as a σπ-diradical to react with a hydrogen atom donor, whereas it displays a zwitterionic reactivity toward weak nucleophiles.

Construction of -Acyliminophosphoranes via Iron(II)-Catalyzed Imidization of Phosphines with -Acyloxyamides.

Employing FeCl as a cheap and readily available catalyst, a facile imidization of phosphines with -acyloxyamides is described, affording synthetically useful acyliminophosphoranes with high functional group tolerance. The transformation is easily performed under an air atmosphere at room temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. The iminophosphoranyl moiety in the product was further utilized as an effective directing group for controllable C(sp)-H bond amidations under Rh(III) catalysis.

Grafting Ink for Direct Writing: Solvation Activated Covalent Functionalization of Graphene.

Covalent functionalization of graphene (CFG) has shown attractive advantages in tuning the electronic, mechanical, optical, and thermal properties of graphene. However, facile, large-scale, controllable, and highly efficient CFG remains challenging and often involves highly reactive and volatile compounds, requiring complex control of the reaction conditions. Here, a diazonium-based grafting ink consisting of only two components, i.

Cobalt-Catalyzed to Geometrical Isomerization of 1,3-Dienes.

An efficient cobalt-catalyzed geometrical isomerization of 1,3-dienes is described. In the combination of a CoCl precatalyst with an amido-diphosphine-oxazoline ligand, the geometrical isomerization of / mixtures of 1,3-dienes proceed in a stereoconvergent manner, affording () isomers in high stereoselectivity. This facile transformation features a broad substrate scope with good functional group tolerance and could be scaled up to the gram scale smoothly with a catalyst loading of 1 mol %.

Lithium and magnesium complexes by using pyridyl-pendanted unsymmetrical β-diketiminates: syntheses and application as catalysts for the hydroboration of carbonyl compounds.

The push for environmentally benign and sustainable chemical processes has reinforced the demand to displace transition metals with cheap, nontoxic and naturally abundant metals. To fulfil this requirement, we endeavored to synthesize alkali- and alkaline earth-metal complexes and employ them as catalysts for organic transformations. Two lithium and one magnesium complexes, which are supported by pyridyl-pendanted unsymmetrical β-diketiminates, have been synthesized and characterized.

A Unified Catalytic Asymmetric (4+1) and (5+1) Annulation Strategy to Access Chiral Spirooxindole-Fused Oxacycles.

A unified catalytic asymmetric (N+1) (N=4, 5) annulation reaction of oxindoles with bifunctional peroxides has been achieved in the presence of a chiral phase-transfer catalyst (PTC). This general strategy utilizes peroxides as unique bielectrophilic four- or five-atom synthons to participate in the C-C and the subsequent umpolung C-O bond-forming reactions with one-carbon unit nucleophiles, thus providing a distinct method to access the valuable chiral spirooxindole-tetrahydrofurans and -tetrahydropyrans with good yields and high enantioselectivities under mild conditions. DFT calculations were performed to rationalize the origin of high enantioselectivity.

One-Pot Synthesis of (Z)-β-Halovinyl Ketones via the Cascade of Sonogashira Coupling and Hydrohalogenation.

Herein, we report an efficient method for the synthesis of (Z)-β-halovinyl ketones through a one-pot Sonogashira coupling and hydrohalogenation reaction promoted by palladium-copper catalyst and Brønsted acid. The ynone intermediates are generated from readily available acid chlorides and terminal alkynes at room temperature, which are directly converted to (Z)-β-halovinyl ketones by treating with triflic acid. This method avoids the use of an external halogen source and features broad substrate scope, high yield, and good to excellent stereoselectivity.