Abstract While gold‐mediated synergistic catalytic processes involving transmetalations with other metals are well understood, Au I /Au III cycles in these reactions rarely reported. Herein a gold‐catalyzed direct alkynylation of cyclopropenes is enabled by two operating cycles, an oxidative cycle alkynyl complex formed addition and one silver‐mediated C−H activation.

Gold(I) complexes are considered active species toward oxidative addition; current understanding indicates a different mechanism in contrast to other late transition metals, but rational of the reactivity profile is lacking. Herein, we propose that accessibility gold(I) center tri- or tetra-coordination critical process involving tetra-coordinate with oxidizing reagent as one ligands an intermediate. A computational study geometry (Phen)R3PAu(I)NTf2 shows such tricoordinate good correlation...

The principle of hard and soft acids bases (HSAB) has given chemists a broad understanding the observed selectivity in variety reaction classes. As we become increasingly aware principle's serious limitations, this study provides an alternative approach. distinction between electrons holes (HSEH) adds to our reactivity. Because radicals are typically better stabilized at sites lone pairs sites, can easily distinguish them. Simple electron density differences (from three single-point...

This work demonstrates the first continuous, stable, and safe operation of organometallic reactions in flow under ambient conditions with high moisture tolerance clogging resistance. The addition deep eutectic solvents (DESs), such as glyceline (choline chloride/glycerol) reline chloride/urea), overcomes previous limitations associated need for cryogenic (long residence times energy requirements) clogging. immiscibility different leads to a segmented where reactive organic substrates are...

Different types of six-membered N-heterocyclic gold carbene complexes were prepared by using gold(I) isonitrile as precursors in combination with suitably functionalized amines. The simple procedures provide an easy access to not only unsymmetrically substituted saturated but rarely reported such oxo-carbene complexes, and partly unsaturated ligands can be obtained following the strategy.

Lithium amides constitute one of the most commonly used classes reagents in synthetic chemistry. However, despite having many applications, their use is handicapped by requirement low temperatures, order to control reactivity, as well need for dry organic solvents and protective inert atmosphere protocols prevent fast decomposition. Advancing development air- moisture-compatible polar organometallic chemistry, chemoselective ultrafast amidation esters mediated lithium reported. Establishing...

A straightforward alkali-metal-mediated hydroamination of styrenes using biorenewable 2-methyltetrahydrofuran as a solvent is reported. Refuting the conventional wisdom incompatibility organolithium reagents with air and moisture, shown here that presence moisture key in favoring formation target phenethylamines over competing olefin polymerization products. The method also compatible sodium amides, latter showing excellent promise highly efficient catalysts under inert atmosphere conditions.

New N-heterocyclic compounds for organic functional materials and their efficient syntheses are highly demanded. A surprising entropy-induced selectivity switch in the gold-catalyzed intramolecular hydroarylation of 2-ethynyl N-aryl indoles was found its exploitation led to straightforward indolo[1,2-a]quinolines. Experimental computational mechanistic investigations gave insight into this uncommon phenomenon special reactivity The high group tolerance methodology enabled access a diverse...

Oxidative carbene organocatalysis, which proceeds via single electron transfer (SET) pathways, has been limited by the moderately reducing properties of deprotonated Breslow intermediates BI-s derived from thiazol-2-ylidene 1 and 1,2,4-triazolylidene 2. Using computational methods, we assess redox potentials based on ten different types known stable carbenes report our findings concerning key parameters influencing steps catalytic cycle. From calculated values first oxidation potential to...

In this study, we report that reacting electron‐rich arenes and benzoic acids with trifluoromethanesulfonic anhydride gives convenient one‐step one‐pot access to triphenylmethylium trifluoromethanesulfonates. This method enables the straightforward formation of these useful Lewis without external C1 sources. Three examples were isolated one preparation upscaled give 3 g trityl salt. Control experiments support a Friedel‐Crafts acylation‐alkylation sequence as mechanism. Interestingly, first...

Abstract Highly strained hydrocarbons have always been a research target of high interest. Due to their untypical electronic structure, they show interesting reactivity patterns and can easily be activated by π‐coordination or insertion reactions with metal complexes. Herein we report the synthesis range 3,3‐disubstituted cyclopropenylgold(I) The such compounds metal, which usually activate cyclopropenes is double‐edged sword. We found σ‐bound vinylic gold generally strong stabilizing effect...

Abstract Während goldkatalysierte synergistische katalytische Prozesse, die Transmetallierung mit anderen Metallen einbeziehen, gut verstanden sind, sind Au I /Au III ‐Zyklen in diesen Reaktionen sehr selten. Hier wird eine direkte Alkinylierung von Cyclopropenen über zwei aktive Katalysezyklen ermöglicht, ein oxidativer Katalysezyklus einem oxidative Addition gebildeten Alkinyl‐Au ‐Komplex, und silbervermittelte C‐H‐Aktivierung.

Reacting (NHC)(cyclopropenyl)gold(I) complexes with cationic gold [(IPr)AuX] afforded extremely reactive allylium-1,1-diido-bridged digold intermediates. We prove the existence and constitution of this structure FT-ICR-MS/MS, NMR, UV–vis–NIR experiments isolated nucleophilic addition product [(Me)(Ph)(CCHC){Au(IPr)}2(SOMe2)]NTf2 DMSO. Our computational investigation unveiled that bonding situation μ-allylium-1,1-diido domain was best described as a three-center–four-electron bond π-backbond....

Abstract A concise and highly stereoselective synthesis of alkynyloxazolines via a gold‐catalyzed domino cyclization‐alkynylation cascade N ‐propargylcarboxamides with benziodoxole reagents is reported. This new protocol, which represents an attractive alternative to two step sequences based on Sonagashira couplings, offers broad substrate scope, excellent functional group tolerance, perfect stereoselectivity. comparison the computed energies isomers product suggests kinetic control as cause...

A sulfilimine-based Group 9 transition-metal-catalysed C-H amidation procedure is reported. Dibenzothiophene-based sulfilimines were shown to constitute a class of novel reagents which enable the transfer wide range N-sulfonyl and N-acyl moieties. It was demonstrated that sulfilimines, are easily accessible from cheap reagents, safe-to-handle represent broadly applicable reagents. The dibenzothiophene can be recycled after use. proceed with high selectivity gave mono-amidated products,...

Abstract Herein we describe a modular, convergent synthesis of substituted benzo[ ]benzo[6,7]‐indolo[2,3‐ h ]carbazoles (BBICZs) using bidirectional gold‐catalyzed cyclization reaction as key step. A building block strategy enabled the easy variation substituents at different positions core structure and general analysis substitution effects on materials properties target compounds. All BBICZs were fully characterized their optical electronic studied experimentally well by computational...

A mechanochemical synthesis of sulfonimidamides by iron(II)-catalyzed exogenous ligand-free N-acyl nitrene transfer to sulfinamides is reported. The one-step method tolerates a wide range with various substituents under solvent-free ambient conditions. Compared its solution-phase counterpart, this approach shows better conversion and chemoselectivity. Mechanistic investigations ESI-MS revealed the generation crucial iron intermediates.

Strong Lewis acids are essential tools for manifold chemical procedures, but their scalable deployment is limited by costs and safety concerns. We report a scalable, convenient, inexpensive synthesis of stable diiminium-based reagents with acidic carbon centre. Coordination pyridine donors stabilises these centres; the 2,2'-bipyridine adduct shows chelation effect at carbon. Due to high fluoride, hydride, oxide affinities, diiminium adducts promising soft hard acids. They effectively produce...

A convenient one-pot approach to bridged heterobimetallic gold(I) palladium(II) bis(acyclic diaminocarbene) complexes is presented. The methodology exploits the graduated nucleophilicities of aliphatic and aromatic amines connected via an unit. This enables a straightforward access from easily available isonitrile metal precursors.

The interaction between murine double minute (MDM2) and p53 is a major target in anticancer drug design. Several potent compound series, including the nutlins spirooxindoles, have previously been established as high-affinity antagonists of MDM2. In this paper, we describe isoindolinone inhibitors with MDM2, characterized by nuclear magnetic resonance spectroscopy. Isoindolinone bind specifically to MDM2 binding site exploit all sub-pockets used p53, spirooxindoles. Furthermore,...

Site-selective functionalization of pyridines is a crucial tool for the synthesis diverse pharmaceuticals and materials. We introduced diiminium pyridine adducts as highly convenient potent Lewis acids. report that tributylphosphine selectively adds to 4-position in tetramethyldiiminium ditrifluoromethanesulfonate, resulting formation title compound. This finding represents an advancement towards utilization units organic reagents or catalysts functionalization. also employ computational...

Abstract A mechanochemical synthesis of sulfonimidamides by iron(II)‐catalyzed exogenous ligand‐free N ‐acyl nitrene transfer to sulfinamides is reported. The one‐step method tolerates a wide range with various substituents under solvent‐free ambient conditions. Compared its solution‐phase counterpart, this approach shows better conversion and chemoselectivity. Mechanistic investigations ESI‐MS revealed the generation crucial iron intermediates.