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In order to explore the different mechanisms possibly occurring in the Au-catalysed cross-coupling of ArN2BF4 and ArB(OH)2 in the presence of CsF, various stoichiometric experiments were performed on gold complexes with (P,N) ligands. Employing 2-pyridylphenyl-diphenylphosphine allowed us to suggest three different mechanistic pathways, starting either with a transmetallation step, via two consecutive single electron transfers, or by implying a transmetallation between Au(I) and Au(III) species. Moreover, when using commercially available chiral (P,N) ligands, the asymmetric formation of atropoisomeric biaryls from suitable aryldiazonium salts and arylboronic acids could be achieved with e.e. up to 26%. [ABSTRACT FROM AUTHOR]

The Cu‐glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF‐8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single‐atom Cu(I) catalyst. Synergy between Cu(I) and ZIF‐8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high‐value‐added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency. [ABSTRACT FROM AUTHOR]

The Cu‐glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF‐8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single‐atom Cu(I) catalyst. Synergy between Cu(I) and ZIF‐8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high‐value‐added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency. [ABSTRACT FROM AUTHOR]

The first example of an enantioselective carbocyclization of an alkyne‐containing substrate catalyzed by chiral Brønsted acids was achieved. The use of the 2‐hydroxynaphthyl substituent on the alkyne as a directing group constituted the key parameter enabling both efficient regioselective protonation of the carbon–carbon triple bond and chiral induction. The key cationic intermediate could be depicted either as a cationic vinylidene ortho‐quinone methide or a stabilized vinyl cation. Atropoisomeric phenanthrenes derivatives were produced in high yields and good enantioselectivities under mild, metal‐free reaction conditions in the presence of chiral N‐triflylphosphoramide catalysts. The carbenic nature of the cationic intermediate was also exploited to describe an example of alkyne/alkane cycloisomerization. [ABSTRACT FROM AUTHOR]

A new class of silicon-based fluoride acceptors with a C-linked heterocycle as the leaving group was synthesized in one step from commercial chemicals, and linked to biomolecules. The resulting conjugates were efficiently 19F-fluorinated in aqueous mixtures, and switching to 18F-labelling provided nucleoside- and peptide-based bioconjugates with excellent molar activities suitable for biological applications. [ABSTRACT FROM AUTHOR]

Production of hydrogen (H 2) from H 2 storage materials is very attractive as a source of sustainable energy. We report that AuNi@ZIF-8 alloys are very efficient nanocatalysts for H 2 evolution upon ammonia borane hydrolysis under visible-light illumination with turnover frequency 3.4 times higher than with the monometallic Ni catalyst in the dark. This improvement is attributed to dramatic volcano-type positive synergy optimized in Au 0.5 Ni 0.5 @ZIF-8, for which ZIF-8 is by far the superior support, as well as to the localized surface plasmon resonance induced between 450 and 620 nm. Infrared spectra analysis and tandem reaction confirm the origin of the hydrogen atoms, reveal the reaction mechanism, and suggest how the cleavage of the B–H and O–H bonds proceeds in this reaction. Deuteration experiments with D 2 O including primary kinetic isotope effects and density functional theory calculation under both dark and visible light conditions show that activation of H 2 O always is the rate-determining step. [Display omitted] • Gold alloys are optimized in ZIF-8 with nickel for very efficient nanocatalysis. • Dramatic synergy between Au and Ni in ZIF-8 for H 2 production catalysis. • ZIF-8 is a far superior support for nanocatalytic H 2 generation by gold nanoalloys. • NiAu@ZIF-8-catalyzed NH 3 BH 3 hydrolysis producing H 2 is boosted by visible light. • NH 3 BH 3 hydrolysis catal by NiAu@ZIF-8 with light produces 3 mol H 2 in 1min45s at rt. [ABSTRACT FROM AUTHOR]