Highly efficient: Pinacol alkylboronates were synthesized by the reaction of tosylhydrazones with bis(pinacolato)diboron or pinacolborane under transition-metal-free conditions. This represents an expeditious conversion carbonyl functionality into a boronate group. Detailed facts importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited typeset. They made available submitted authors. Please note: The publisher is responsible...

Oxidative C-H/C-H coupling is a promising synthetic route for the streamlined construction of conjugated organic materials optoelectronic applications. Broader adoption these methods nevertheless hindered by need catalysts that excel in forging core semiconductor motifs, such as ubiquitous oligothiophenes, with high efficiency absence metal reagents. We report (thioether)Pd-catalyzed oxidative method rapid assembly both privileged oligothiophenes and challenging cases, even at low catalyst...

Thioether ancillary ligands have been identified that can greatly accelerate the C–H alkenylation of O-, S-, and N-heteroarenes. Kinetic data suggest thioether–Pd-catalyzed reactions be as much 800× faster than classic ligandless systems. Furthermore, mechanistic studies revealed bond cleavage turnover-limiting step, rate acceleration upon thioether coordination is correlated to a change from neutral cationic pathway for this key step. The formation cationic, low-coordinate catalytic...

An efficient synthesis of pyrrole derivatives is achieved via ordered isocyanide insertion reaction, driven by ring strain and mediated intramolecular non-covalent bonds. This method harnesses the strategic design of...

Abstract Intramolecular aromatic substitution and Büchner reaction have been established as powerful methods for the construction of polycyclic compounds. These reactions are traditionally catalyzed by Rh II catalysts with α‐diazocarbonyl compounds substrates. Herein a transition‐metal‐free intramolecular substitution/Büchner is presented. use readily available N ‐tosylhydrazones diazo compound precursors show wide substrate scope.

Revitalisierung durch Sauerstoff: Eine Rhodium(III)-katalysierte Sequenz aus oxidativer C-H/N-H-Aktivierung und Anellierung eröffnet den Zugang zu substituierten 1,2-Benzothiazinen ausgehend von leicht verfügbaren NH-Sulfoximinen Alkinen (siehe Schema; Cp*=C5Me5). Das Oxidationssystem besteht molekularem Sauerstoff einer katalytischen Menge Fe(OAc)2. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed...

A Pd-catalyzed stereoselective synthesis of 3-vinylindoles and 3-vinylbenzofurans has been developed. The reaction merges the alkyne-based cyclization Pd carbene migratory insertion in a single catalytic cycle, generating C–C bond C═C double one operation.

Abstract This review analyzes recent mechanistic studies that have provided new insights into how the structure of a metal complex influences rate and selectivity base‐assisted C−H cleavage. Partitioning broader continuum classes delimited by polarization between catalyst substrate during cleavage is postulated as method to identify catalysts favoring electrophilic or nucleophilic reactivity patterns, which may be predictive based on structural features (i. e., oxidation state, d‐electron...

Hoch effizient: Pinakolalkylboronate wurden durch die Umsetzung von Tosylhydrazonen mit Bis(pinakolato)dibor oder Pinakolboran ohne Zusatz Übergangsmetallverbindungen erhalten. Mit dieser Reaktion gelingt zügige Umwandlung einer Carbonylfunktion in eine Boronatgruppe. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: The...

Substituted 1,3-dienes are valuable synthetic intermediates used in myriad catalytic transformations, yet modern methods for their preparation a highly modular fashion using simple precursors relatively few. We report here an aerobic boron Heck reaction with cyclobutene that forms exclusively linear 1-aryl-1,3-dienes (hetero)arylboronic acids, or 1,3,5-trienes alkenylboronic rather than typical products (i.e., substituted cyclobutenes). Experimental and computational mechanistic data support...

1<italic>H</italic>-Indazoles have been synthesized from readily available <italic>N</italic>-tosylhydrazones and nitroaromatic compounds under mild reaction conditions.

A palladium-catalyzed decarboxylative α-allylation of thiazolidinones and azlactones with aza-π-allylpalladium zwitterionic intermediates, in situ generated from sulfonamido-substituted allylic carbonates, is successfully developed. This method allows the formation a series structurally diverse 5-alkylated 2-piperidones under mild conditions moderate to high yields (up 99% yield).

Abstract Intramolecular aromatic substitution and Büchner reaction have been established as powerful methods for the construction of polycyclic compounds. These reactions are traditionally catalyzed by Rh II catalysts with α‐diazocarbonyl compounds substrates. Herein a transition‐metal‐free intramolecular substitution/Büchner is presented. use readily available N ‐tosylhydrazones diazo compound precursors show wide substrate scope.

The origin of switchable site selectivity during Pd-catalysed C-H alkenylation heteroarenes has been examined through More O'Ferrall-Jencks, isotope effect, and DFT computational analyses, which indicate substitution ionic thioether for pyridine dative ligands induces a change from selectivity-determining cleavage to C-C bond formation, respectively.

1,4-Benzodiazepin-5-ones were synthesized in 71–89% yields from 2-isocyanato-<i>N</i>-(2-oxoalkyl)benzamides via a new catalytic intramolecular aza-Wittig reaction. Starting easily accessible phthalic anhydride and α-arylamino ketones, the corresponding 2-{[(2-oxoalkyl)amino]carbonyl}benzoic acids underwent sequential formation of acid azide Curtis rearrangement to give that reacted directly final 2,4-diaryl-3,4-dihydro-5<i>H</i>-1,4-benzodiazepin-5-ones...

The acetate derivatives of coumarin exhibited a prominent turn-on type signaling behavior toward BO(3)(-) ions over other common anions. Signaling is based on the selective deprotection groups by perborate, which resulted in significant fluorogenic an buffered solution (pH 5.0). Interestingly, detection process makes raw material 7-hydroxycoumarin regenerate, and probe could be applied for thimerosal. Furthermore, optical properties its BO(3)(-)-induced product were theoretically studied...

Liver cancer is generally considered the leading cause of deaths worldwide, and hepatocellular carcinoma (HCC) contributes to more than 90% liver cancers. The altered lipid metabolism for rapid cell growth tumor formation has been frequently proven. In this study, an ambient ionization mass spectrometry technique, evaporative (REIMS) using a monopolar electric knife, called iKnife, was systematically optimized employed ex vivo analysis 12 human HCC tissue specimens together with paired...

5-Carboxamide-oxazolines were synthesized via a Passerini 3CC-Staudinger-aza-Wittig sequence in moderate to good yields, starting from easily accessible chloroacetaldehyde, isocyanides, and various acids.

Abstract Herein, we report the synthesis of a series π‐expanded coumarin derivatives by selective C−H alkenylation β‐naphthol in presence palladium catalyst. The use an anionic thioether ligand is critical for ensuring high reactivity this reaction; it enables low catalyst loadings, mild reaction conditions, and acetic acid as green solvent. This chemistry widely applicable to naphthol‐based aromatic substrates bearing either electron‐donating or ‐withdrawing functional groups. magnified image