The electrochemical reduction of CO2 into renewable chemical products such as formic acid is an important and challenging goal. Traditional Pd catalysts suffer from CO poisoning, which leads to current density decay short operating lifetimes. Here we explored the ability control nanoparticle surface morphology amplify catalytic activity increase stability in electroreduction formate. Through computational studies have elucidated trends intermediate binding govern selectivity activity. We...

The organization of nanoparticles in constrained geometries is an area fundamental and practical importance. Spherical confinement nanocolloids leads to new modes packing, self-assembly, phase separation relaxation colloidal liquids; however, it remains unexplored research for liquid crystals. Here we report the cholesteric crystal formed by nanorods spherical droplets. For suspensions cellulose nanocrystals, with progressive confinement, observe into a micrometer-size isotropic droplet core...

ConspectusThe oxindole scaffold is a privileged structural motif that found in variety of bioactive targets and natural products. Moreover, derivatives the structure are widely present number biologically relevant compounds key intermediates synthesis diverse products pharmaceuticals. Therefore, novel methods to obtain oxindoles remain high priority synthetic organic chemistry.Over past several decades, transition-metal-catalyzed methodologies have been applied toward heterocycles. A...

Copper-catalyzed enantio- and diastereoselective conjugate borylation across Michael acceptors, with subsequent Mannich-type cyclization, was utilized to construct tetrahydroquinoline scaffolds containing three contiguous stereocenters.

A rhodium-Josiphos(L*) catalyzed enantioselective intramolecular hydroarylation reaction is described. The reductive cyclization of o-bromoaniline-derived acrylamides provides convenient access to 3,3-disubstituted oxindoles in good yields and with excellent enantioselectivity across a range substrates. We propose that the key proceeds via rhodium(III) intermediate. Overall, this method represents an unusual mode reactivity for rhodium catalysis complementary palladium(0)-catalyzed...

Abstract Acyl substituted triazoles are valuable scaffolds, but the direct synthesis of these moieties from terminal alkynes by copper catalysis remains unexplored. We report a robust, general, and efficient method using simple CuI/2,2′‐bipyridine catalytic system. This transformation involves catalyzed azide‐alkyne cycloaddition (CuAAC) followed an intramolecular acylation onto carbamoyl chloride. The reaction proceeds under mild conditions, tolerates several functional groups, is readily...

Fundamental studies and practical use of metal nanoparticles (NPs) frequently depend on the ability to reproducibly synthesize large quantities shape-specific NPs. For this reason, facile synthetic procedures are desired that will lead uniformly sized NPs exhibiting specific shapes. Here, we report a general approach large-scale synthesis noble nanocrystals having well-defined shapes narrow size distribution. This method utilizes seed-mediated NP growth in aqueous suspensions cationic...

We report here a proof-of-concept for the cleavage of unstrained remote Csp3–Csp3 bonds at room temperature assisted by directing group, opening up new possibilities to use aliphatic carboxylic acids as suitable alkenyl coupling partners. This strategy involves Pd-mediated Csp3–H activation directed tethered 8-aminoquinoline followed concerted asynchronous carbene insertion into Pd–C bond, and an unexpected β-carbon–carbon bond splitting. The partner is novel route promote C–C cleavage,...

Abstract A rhodium‐Josiphos(L*) catalyzed enantioselective intramolecular hydroarylation reaction is described. The reductive cyclization of o ‐bromoaniline‐derived acrylamides provides convenient access to 3,3‐disubstituted oxindoles in good yields and with excellent enantioselectivity across a range substrates. We propose that the key proceeds via rhodium(III) intermediate. Overall, this method represents an unusual mode reactivity for rhodium catalysis complementary palladium(0)‐catalyzed...

A Ni-catalyzed C–S cross-coupling using only NiI2 (0.5–2.5 mol%) and P(OiPr)3 (2.0–10.0 is reported. Using an air-stable Ni(II) precatalyst, a cheap commercially available ligand, scalable robust method was developed to cross-couple various thiophenols styryl bromides, including some sterically encumbered thiols, α-bromocinnamaldehyde as well thiolation-cyclization.

The rhodium-catalyzed asymmetric ring opening reaction of oxabicyclic alkenes is shown to be an efficient method for synthesizing chiral heterocycles. We demonstrate that the pairwise combination catalyst with amino-acid-derived pronucleophiles results in a stereodivergent synthesis diastereomeric hydroxyesters. A favorable conformational preference induces subsequent lactonization one diastereomer leading highly enantioselective oxazinones.

Adrenocorticotropic hormone (ACTH) plays an essential role in regulating corticosteroid production, which has important functions a myriad of critical physiological functions. In this proof-of-concept study, miniaturized immunosensor was developed for the highly sensitive detection ACTH using electrochemical impedance spectroscopy (EIS) connection with disposable screen-printed gold electrodes (SPGEs). A film 3,3′-dithiobis[sulfosuccinimidylpropionate] (DTSSP) prepared to immobilize...

Abstract Acyl substituted triazoles are valuable scaffolds, but the direct synthesis of these moieties from terminal alkynes by copper catalysis remains unexplored. We report a robust, general, and efficient method using simple CuI/2,2′‐bipyridine catalytic system. This transformation involves catalyzed azide‐alkyne cycloaddition (CuAAC) followed an intramolecular acylation onto carbamoyl chloride. The reaction proceeds under mild conditions, tolerates several functional groups, is readily...

The utilization of the Bpin group as a pronucleophile to facilitate assembly cyclic carbamates has been achieved. This one-pot process involves an initial copper-catalyzed borylation, subsequent C–B bond oxidation generate reactive alcohol intermediate, and cyclization. We report use this efficient, scalable, simple method toward synthesis wide range benzoxazinone scaffolds, including enantioselective results. Subsequent transformations into useful scaffolds showcase utility strategy.

We report a rhodium-catalyzed domino strategy for the preparation of oxindole-containing products starting from simple ortho-bromoaniline-derived acrylamides. Mechanistic and computational studies demonstrate that reaction initially proceeds through Heck-type process to generate benzylidene intermediate via β-hydride elimination. Subsequently, RhI–hydride species is generated in situ forms final oxindole 1,4-conjugate addition hydride. Key success use sodium formate as it enables generation...

A reductive cyclization to prepare a variety of N-heterocycles, through the use ortho-vinylanilides, is reported. The reaction catalyzed by an inexpensive and bench-stable iron complex generally occurs at ambient temperature. transformation likely proceeds hydromagnesiation vinyl group, trapping in situ generated benzylic anion intramolecular electrophile form heterocycle. This iron-catalyzed strategy was shown be broadly applicable utilized synthesis substituted indoles, oxindoles...

Investigations of saturated spirocycles toward selective C–H functionalization reactions are scarce, despite their potential applications. In this work, we uncovered fundamental reactivity and selectivity differences between heterocycles spirocyclic analogues using a model radical xanthylation coupled with computational analysis. Ultimately, study sheds light on the fundamental, understudied spirocycles, thereby allowing for pronounced chemical tunability that will prove to be advantageous...

Abstract A reductive cyclization to prepare a variety of N ‐heterocycles, through the use ortho ‐vinylanilides, is reported. The reaction catalyzed by an inexpensive and bench‐stable iron complex generally occurs at ambient temperature. transformation likely proceeds hydromagnesiation vinyl group, trapping in situ generated benzylic anion intramolecular electrophile form heterocycle. This iron‐catalyzed strategy was shown be broadly applicable utilized synthesis substituted indoles,...