A novel asymmetric nickel‐based procedure has been developed in which CO2 fixation is achieved as a second step of a truncated Heck coupling. For this, a new chiral ligand has been prepared and shown to achieve enantiomeric excesses up to 99 %. The overall process efficiently furnishes chiral 2,3‐dihydrobenzofuran‐3‐ylacetic acids, an important class of bioactive products, from easy to prepare starting materials. A combined experimental and computational effort revealed the key steps of the catalytic cycle and suggested the unexpected participation of Ni(I) species in the coupling event.

The preparation of symmetrical (hetero)biaryls via arylazo sulfones has been successfully carried out upon visible light irradiation in the presence of PPh 3 AuCl as the catalyst. The present protocol led to the efficient synthesis of a wide range of target compounds in an organic-aqueous solvent under photocatalyst-free conditions.

New chiral BINOL‐based phosphate counterions have been synthesized, fully characterized, and employed in the enantioselective gold‐catalyzed dearomatization of β‐naphthols with allenamides. A range of densely functionalized C1‐allylated naphthalenones were realized under mild conditions and high levels of chemo‐, regio‐ and stereoselectivity (ee up to 95 %).

A carboxylative Ni-catalyzed tandem C-C σ-bond activation of cyclobutanones followed by CO2-electrophilic trapping is documented as a direct route to synthetically valuable 3-indanone-1-acetic acids. The protocol shows an adequate functional...

A series of modular ImPy−carbene−Au(I) complexes are synthesized and fully characterized both in the solid state and in solution. The presence of oligoaryl units (phenyl and thienyl rings) at the C5-position of the ImPy core (in close proximity to the gold center) imprints on the organometallic species fine-tunable and predictable catalytic properties. A marked accelerating effect was recorded in several [Au(I)]-catalyzed electrophilic activations of unsaturated hydrocarbons when a CF 3 -containing aromatic ring was accommodated at the ImPy core.

A novel gold(i)-catalyzed protocol for the synthesis of 4H-1,3-dioxin-3-ones is presented.

A new [Au(I)] catalyzed intramolecular hydrocarboxylation of allenes is presented as a valuable synthetic route to oxazino-indolones. The employment of 3,5-(CF3)2-C6H3-ImPyAuSbF6 as the optimal catalyst (5 mol%) was necessary to...

The enantioselective 1,3-dipolar cycloaddition of nitrones and arylpropionaldehydes to generate highly functionalized scaffolds for application in drug discovery was herein investigated. The use of a second-generation MacMillan catalyst as hydrochloride salt consistently accelerated the reaction speed, allowing a decrease in the reaction time up to >100 times, still affording 4-isoxazolines with good to excellent enantiomeric ratios at room temperature. As a proof of concept, further functionalization of the isoxazoline core through Pd-catalyzed cross-coupling was performed, generating differently functionalized chemical architectures in high yield.