Abstract We describe a novel, short, and flexible approach to diverse N‐doped polycyclic aromatic hydrocarbons (PAHs) through gold‐catalyzed π‐extension of anthranils with o ‐ethynylbiaryls as reagents. This strategy uses easily accessible starting materials, is simple due high step atom economy, shows good functional‐group compatibility well scale‐up potential. Mechanistically, the tandem reaction proposed involve nucleophilic addition/ring opening/regiospecific C−H...

Abstract A facile, site‐selective, and divergent approach to construct 2‐aminopyrroles quinoline‐fused polyazaheterocycles enabled by a simple gold(III) catalyst from ynamides anthranils under mild reaction conditions is described. This one‐pot strategy uses readily available starting materials, proceeds in highly step‐ atom‐economical manner, with broad substrate scope scale‐up potential. The key element for success this tandem catalyst‐directed preferred quenching of the situ generated...

A novel and atom-economical synthesis of fully substituted 4-aminoimidazoles via gold-catalyzed selective [3 + 2] annulation 1,2,4-oxadiazoles with ynamides is reported. This protocol represents a new strategy to access α-imino gold carbenes, which corresponds an unprecedented intermolecular transfer N-acylimino nitrenes ynamides. Moreover, the reaction proceeds 100% atom economy, exhibits good functional group tolerance, can be conducted in gram scale.

Abstract Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic derivatives in decarboxylative couplings has proven be a valuable tool for construction C−C C‐heteroatom bonds. This synthetic strategy provides complementary bond disconnection traditional cross‐coupling methods. In this review, we provide comprehensive overview decarboxylation‐initiated intermolecular formation, outlining several main...

Considering the indispensable significance and utilities of meta-substituted pyridines in medicinal, chemical as well materials science, a direct meta-selective C-H functionalization is paramount importance, but such reactions remain limited highly challenging. In general, established methods for meta rely on utilization tailored electrophilic reagents to realize intrinsic polarity match. Herein, we report complementary electrochemical methodology; diverse nucleophilic sulfinates allow...

The development of practical and selective strategies for deuterium incorporation to construct deuterated molecules, particularly deuterium-labeled amino acids, has become as a growing focus basic research, yet it remains formidable challenge. Herein, we present bioinspired calcium-HFIP-mediated site-selective reductive deutero-amination α-oxo-carbonyl compounds with amines. Utilizing d2-Hantzsch ester the source, this reaction attains remarkable deuteration efficiency (> 99% deuteration)....

1,3,5-Triazinanes serve as surrogates for 1,4-dipoles in gold-catalyzed formal 4+2 cycloadditions.

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient powerful tool for the synthesis diverse valuable amine derivatives relevance medicinal chemistry, biochemistry, material science. Among these developed carboamination methodologies, direct use C–H activation strategy leverage process is particularly attractive due ubiquity such bonds in organic molecules. In this review, we provide overview development intermolecular across C–C...

The electrochemical methods for asymmetric indolization are still elusive and pose a significant challenge. Taking advantage of 2-alkynylanilines as electrochemically compatible indolyl equivalents, we herein represent mild highly enantioselective electrocatalytic process tandem C–H to form 2,3′-biindolyl atropisomers along with hydrogen evolution reaction. Integrated experimental computational mechanistic studies revealed that sequential metalation/nucleophilic cyclization/reductive...

Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination cyclization of terminal alkynes with organoboronic acids anthranils for facile modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent redox buffer suppress the generation off-cycle Ni(0) complex. Moreover, anionic acetylacetonate (acac) ligand was found be vital ensure productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.

Abstract Wir beschreiben einen neuen, kurzen und flexiblen Weg zu verschiedenen N‐haltigen polycyclischen aromatischen Kohlenwasserstoffen (PAK) über eine goldkatalysierte π‐Erweiterungsreaktion von Anthranilen mit o ‐Ethinylbiarylen als Reagenzien. Diese Strategie nutzt leicht zugängliche Edukte, ist aufgrund einer hohen Stufen‐ Atomökonomie einfach zeigt gute Toleranz gegenüber funktionellen Gruppen, ein Hochskalieren ebenfalls möglich. Der mechanistische Vorschlag für die Tandemreaktion...

A novel asymmetric ring-opening reaction of N-substituted azabenzonorbornadienes with a wide variety substituted benzyl alcohols and the addition thiols are reported, affording corresponding 1,2-trans-alkoxyamino products in moderate yields excellent enantioselectivities (up to 94% ee) thiol high lower enantiomeric excesses (ee) presence iridium catalyst, respectively. The effects ligands, catalyst loading, solvents additives, temperature were also investigated. anti-configuration product 3c...

Abstract A gold‐catalyzed intermolecular [4+2] annulation of easily accessible 2‐ethynylanilines with ynamides offers a highly region‐selective, modular, efficient, and atom‐economical strategy for the synthesis substituted 2‐aminoquinolines in up to 93% yield. magnified image

2,2′-Biaryldicarboxylates are important functionalities in bioactive compounds, functional materials, and chiral catalysts. These compounds have been found to be conveniently accessible from benzoic acids via Rh-catalyzed electrooxidative C–H/C–H couplings, giving valuable dihydrogen as the byproduct. In an undivided cell with Pt electrodes, RhCl3·3H2O catalyzes oxidative carboxylate-directed ortho-homocoupling of various aromatic a current efficiency 67%. The protocol is operationally...

An exogenous electrolyte- and base-free electrochemical cobalt-catalysed atroposelective C–H annulation has been established to construct N–N axially chiral isoquinolinones in excellent enantioselectivities good yields.

A new, versatile, and highly efficient nickel-catalyzed asymmetric ring-opening (ARO) reaction of oxabenzonorbornadienes with a wide variety arylboronic acids has been developed, yielding cis-2-aryl-1,2-dihydronaphthalen-1-ols in high yields (up to 99%) good excellent enantioselectivities 99% ee) under very mild conditions. The effects various nickel precursors, chiral bidentate ligands, catalyst loadings, bases, solvents, temperatures on the yield enantioselectivity were also investigated....

Abstract A facile, site‐selective, and divergent approach to construct 2‐aminopyrroles quinoline‐fused polyazaheterocycles enabled by a simple gold(III) catalyst from ynamides anthranils under mild reaction conditions is described. This one‐pot strategy uses readily available starting materials, proceeds in highly step‐ atom‐economical manner, with broad substrate scope scale‐up potential. The key element for success this tandem catalyst‐directed preferred quenching of the situ generated...

Palladium-catalyzed couplings of silicon enolates with aryl electrophiles are great synthetic utility, but often limited to expensive bromide substrates. A comparative experimental study confirmed that none the established ligand systems allows couple inexpensive chlorides α-trimethylsilyl alkylnitriles. In contrast, ylide functionalized phosphines (YPhos) led encouraging results. statistical model was developed correlates reaction yields features. It employed predict catalyst structures...

A mild and general protocol involving amnio- oxyselenation of diverse alkenes for the efficient synthesis organo-Se compounds is achieved via an environmentally benign calcium-catalyzed three-component reaction. This selenofunctionalization reaction exhibits excellent substrate/functional group tolerance high levels chemo- regioselectivity. Its utility was exemplified in late-stage functionalization even aggregation-induced emission luminogen labeling compounds.

A calcium-mediated three-component selenylation of gem-difluoroalkenes using alcohols as nucleophiles and N-(phenylseleno)phthalimide the agent has been developed for efficient synthesis various α,α-difluoroalkyl-β-selenides. This reaction exhibits broad substrate functional group tolerance, along with high levels chemo- regioselectivity. Additionally, synthetic utility transformation in late-stage functionalization drug molecules was demonstrated.

Rh( iii )-catalyzed redox-neutral C–H [4 + 1] annulation of sulfoximines with α,α-difluoromethylene alkynes has been realized to diastereoselectively build E -monofluoroalkenyl benzoisothiazole 1-oxides.

A green method has been established by employing gem -difluorocyclopropylenes as versatile building blocks, leading to the chemodivergent formation of several fluorinated structural motifs including cyclopropapyrazolopyridines, indolizines etc .