A nickel-catalyzed asymmetric reductive hydroarylation of vinyl amides to produce enantioenriched α-arylbenzamides is reported. The use a chiral bisimidazoline (BIm) ligand, in combination with diethoxymethylsilane and aryl halides, enables the regioselective introduction groups internal position olefin, forging new stereogenic center α N atom. neutral reagents mild reaction conditions provides simple access pharmacologically relevant motifs present anticancer, SARS-CoV PLpro inhibitors,...

The use of electrophilic cyanide-transfer reagents has become a versatile strategy to access important structural motives in complementary way compared other methods.

Cycloadditions of epoxides with CO2 to synthesize cyclic five-membered ring organic carbonates are broad interest from a synthetic, environmental, and green chemistry perspective, the development effective catalysts for these transformations is an ongoing challenge. A series eight charge-containing thiourea salts that catalyze reactions under mild conditions (i.e., 60 °C atmospheric pressure) reported. Substrate scope mechanistic studies were also carried out, isotope effects measured,...

Novel densely functionalized β^2,2-amino acids were obtained in almost enantiopure form using down to 20 ppm of a chiral phase-transfer catalyst.

This communication describes the first proof of concept for an asymmetric α-cyanation β-ketoesters using a hypervalent iodine-based electrophilic cyanide-transfer reagent. A series different organocatalysts has been investigated and it was found that use naturally occurring Cinchona alkaloids allows obtaining target products in good yields with moderate enantioselectivities up to er = 76:24 under operationally simple conditions.

A detailed study of literature-known and novel S-containing pincer-type ligands for ruthenium-catalyzed homogeneous hydrogenation dehydrogenation reactions was carried out. The scope limitations these catalysts were carefully investigated, it shown that simple bench-stable SNS–Ru complexes can be used to facilitate the a variety different substrates at maximum H2 pressure 20 bar under operationally simple, easy scale up, glovebox-free conditions by using starting materials reagents do not...

A novel class of (P^N^C) pincer ligands capable stabilizing elusive gold(III) species is reported here. Straightforward access to (P^N^C)gold(III) hydroxo, formate, and hydride complexes has been streamlined by first incorporating a cycloauration step devoid toxic metals or harsh conditions. The resulting gold exhibit remarkable stability in solution as well the solid state under ambient conditions, which enabled their characterization X-ray diffraction analyses. Interestingly, influence...

The release of bromine radicals from a nickel complex via homolytic cleavage under visible light allows the activation alkyl boronic acids, which participate in Suzuki–Miyaura cross-coupling process batch and continuous flow settings.

Alkyne hydrofunctionalizations are a powerful strategy to efficiently build up structural complexity. The selectivity of these reactions is typically governed by the interaction between alkyne and metal-hydride, which commonly proceeds via well-understood syn-insertion mechanism. In contrast, anti-insertions far less common, with proposed mechanisms often extrapolated from literature precedents rather than grounded in direct experimental evidence. While gold complexes rank among most...

Detailed investigations concerning the organocatalytic (asymmetric) α-azidation of prochiral β-ketoesters were carried out. It was shown that racemic version such a reaction can either be out under oxidative conditions using TMSN₃ as azide-source with quaternary ammonium iodides catalysts, or by hypervalent iodine-based electrophilic azide-transfer reagents different organocatalysts. In addition, latter strategy could also modest enantioselectivities when simple cinchona alkaloid albeit...

Abstract A nickel‐catalyzed asymmetric reductive hydroarylation of vinyl amides to produce enantioenriched α‐arylbenzamides is reported. The use a chiral bisimidazoline (BIm) ligand, in combination with diethoxymethylsilane and aryl halides, enables the regioselective introduction groups internal position olefin, forging new stereogenic center α N atom. neutral reagents mild reaction conditions provides simple access pharmacologically relevant motifs present anticancer, SARS‐CoV PLpro...

Unsymmetrical 1,3-diynes can easily be accessed under catalyst-free conditions by reacting terminal alkynes with hypervalent iodine-based electrophilic alkyne-transfer reagents.

A detailed screening of differently substituted chiral and achiral (thio)urea-containing quaternary ammonium salts revealed their potential as catalysts for the CO2-fixation with epoxides to obtain cyclic carbonates in high yields under operationally simple atmospheric pressure conditions. Additional DFT calculations substantiate a mechanism involving an initial addition nucleophilic iodide counter anion salt H-bonding activated epoxide, followed by stepwise cyclization.

A chelation-assisted oxidative addition of gold(i) into the C-C bond biphenylene is reported here. The presence a coordinating group (pyridine, phosphine) in unit enabled use readily available halide precursors providing new, straightforward entry towards cyclometalated (N^C^C)- and (P^C)-gold(iii) complexes. Our study, combining spectroscopic crystallographic data with DFT calculations, showcases importance neighboring, weakly groups successful activation strained bonds by gold.

We herein report an unprecedented strategy for the asymmetric α-chlorination of β-keto esters with hypervalent iodine-based Cl-transfer reagents using simple Cinchona alkaloid catalysts. Our investigations support mechanism where species serves as a nucleophilic catalyst by reacting chlorinating agent to generate chiral electrophilic reagent in situ. Using at least 20 mol-% allows good yields and enantioselectivities variety different under operationally conditions.

We herein report a protocol for the asymmetric aldol-initiated cascade addition of isoxazolidin-5-ones to ortho-cyanobenzaldehydes by using Takemoto's bifunctional organocatalyst. This approach allows synthesis various novel β2,2-amino acid-phthalide conjugates with good enantio- and diastereoselectivities in reasonable yields further ring-opening these compounds acyclic carboxylic acid derivatives was demonstrated too.