Decarbonylative Pd-Catalyzed Suzuki Cross-Coupling for the Synthesis of Structurally Diverse Heterobiaryls.

Heteroaromatic biaryls are core scaffolds found in a plethora of pharmaceuticals; however, their direct synthesis by the Suzuki cross-coupling is limited to heteroaromatic halide starting materials. Here, we report a direct synthesis of diverse nitrogen-containing heteroaromatic biaryls by Pd-catalyzed decarbonylative Suzuki cross-coupling of widely available heterocyclic carboxylic acids with arylboronic acids. The practical and modular nature of this cross-coupling enabled the straightforward preparation of >45 heterobiaryl products using pyridines, pyrimidines, pyrazines, and quinolines in excellent yields. We anticipate that the modular nature of this protocol will find broad application in medicinal chemistry and drug discovery research.

Expanded Ring NHC Silver Carboxylate Complexes as Efficient and Reusable Catalysts for the Carboxylative Cyclization of Unsubstituted Propargylic Derivatives.

Stabilized by a bulky N-heterocyclic carbene [BP DPr, 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene] ligand, new silver carboxylate complexes of the form BP DPrAgO2 C-R (R=Me, Ph) have been synthesized and fully characterized in solution and in the solid state and implemented as sole catalysts (base-, additive-, and, in some cases, solvent-free) in the challenging fixation of carbon dioxide to unsubstituted propargylic derivatives for the synthesis of oxazolidinones and α-methylene cyclic carbonates. Derived from X-ray diffraction studies, the molecular geometry and the concept of buried volume were employed to describe the structural and steric features of these silver complexes. Their stability and efficiency as catalysts have been demonstrated by the synthesis of 29 carboxylation products (72-98 % yield) at low catalyst loadings (0.01-1.5 mol%). Characteristics are high turnover numbers (up to 9400), catalyst recyclability (up to 96 % yield after the 7th cycle with no decomposition of the silver complex), and the possibility to scale-up the reaction.

Sterically Demanding AgI and CuI N-Heterocyclic Carbene Complexes: Synthesis, Structures, Steric Parameters, and Catalytic Activity.

The synthesis and full characterization of new air-stable AgI and CuI complexes bearing structurally bulky expanded-ring N-heterocyclic carbene (erNHC) ligands is presented. The condensation of protonated NHC salts with Ag2 O afforded a collection of AgI complexes, and their first use as ligand transfer reagents led to novel isostructural CuI or AuI complexes. In situ deprotonation of the NHC salts in the presence of a copper(I) source, provides a library of new CuI complexes. The solid-state structures feature large N-CNHC -N angles (118-128°) and almost identical angles between the aryl groups on the nitrogen atoms and the plane of the N-C-N unit of the carbene (i.e. torsion angles close to 0°). Among the steric parameters, the percent buried volume (%Vbur ) values span easily in the 50-57 % range, and that one of (9-Dipp)CuBr complex (%Vbur =57.5) overcomes to other known erNHC-metal complexes reported to date. Preliminary catalytic experiments in the copper-catalyzed coupling between N-tosylhydrazone and phenylacetylene, afforded 76-93 % product at the 0.5-2.5 mol % catalyst loading, proving the stability of CuI erNHC complexes at elevated temperatures (100 °C).

Gold(I) Complexes Stabilized by Nine- and Ten-Membered N-Heterocyclic Carbene Ligands.

Nine- and ten-membered N-heterocyclic carbene (NHC) ligands have been developed and for the first time their gold(I) complexes were synthesized. The protonated NHC pro-ligands 2 a-h were prepared by the reaction of readily available N,N'-diarylformamidines with bis-electrophilic building blocks, followed by anion exchange. In situ deprotonation of the tetrafluoroborates 2 a-h with tBuOK in the presence of AuCl(SMe2 ) provided fast access to NHC-gold(I) complexes 3-10. These new NHC-gold(I) complexes show very good catalytic activity in a cycloisomerization reaction (0.1 mol % catalyst loading, up to 100 % conversion) and their solid-state structures reveal high steric hindrance around the metal atom (%Vbur up to 53.0) which is caused by their expanded-ring architecture.

Solvent effect in the polyethylene recovery from multilayer postconsumer aseptic packaging.

Polyethylene films were separated and recovered from polyethylene-aluminum composites derived from recycling multilayer postconsumer aseptic packaging. A brief study about the separation process by dissolving PE-aluminum (PE-Al) composites into a series of organic solvents with a combination of time and temperature is presented. Through this procedure, 56% polyethylene is recovered from this kind of composites in optimized conditions. DSC and TGA studies were performed to determine the thermal stability of recovered polyethylene films and to establish a comparison with a PE reference commercial product, demonstrating that recovered polyethylene films kept their thermal properties.