The first "in air" copper-catalyzed method for the selective synthesis of tri-and tetrasubstituted vinylboronate derivatives is presented. Three different variants of the borylation of internal alkynes (α-hydroboration, β-hydroboration, and carboboration) are described using a single catalyst: [Cu(Cl)(IMes)] (IMes = N,N′-bis-[2,4,6-(trimethyl)phenyl]imidazol-2-ylidene) without taking any precaution to avoid the presence of air. Bis(pinacolato)diboron was used to afford β-hydroborated products in the presence of methanol. Adding instead another electrophile allowed the formation of tetrasubstituted vinylboronate species. Finally, the α-products were obtained using pinacolborane as the boron source. All compounds were obtained in high yield with excellent regioselectivity at low catalyst loading (0.04−2 mol %). The protocol constitutes a very convenient route to access these highly valuable molecules.

Thes ynthesis andc haracterization of abnormal N-heterocyclic carbene,c yclic (alkyl)(amino)carbene,a nd mesoionic carbene copper(I) complexesa re reported.T hese organometallic species are obtained via aversatile and inexpensive synthetic pathwayu sing readily available reactants,n amely copper oxide andi miniums alts.T he catalytic activity of this series of complexes was evaluated in the [3+ +2] cycloaddition of alkynes with azides (CuAAC). Outstanding catalytic properties were observed for the abnormal NHC-a nd triazolylidenebased copper(I) complexes.

We report the first example of BAC-Cu complex (BAC = bis(diisopropylamino)cyclopropenylidene) and its use as a carbene-transfer reagent, allowing access to Au-, Pd-, Ir-and Rh-BAC compounds. Catalytic experiments show the high activity of the [CuCl(BAC)] complex in Click chemistry.

MFI-type materials with a lamellar morphology were successfully synthesized by using mononitrogen surfactants specifically designed by molecular modelling. The mononitrogen surfactants directed the recrystallization of a crystalline layered polysilicate formed in situ, the magadiite, into a zeolite ZSM-5.Moreover, the surfactants allow the preservation of the lamellar shape of the magadiite and inhibit a further growth into one dimension, leading to the formation of zeolite ZSM-5 nanosheets with a thickness comprised between 2 and 3 nm and a Si/Al ratio of 24. This simple approach paves a new way for obtaining zeolite materials of controlled size and shape for specific catalytic applications.

The synthesis of the four olefin metathesis precatalysts Caz-1a-d, featuring the NHC ligand N,N'-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) and four different phosphites (P((OPr)-Pr-i)(3), P(OPh)(3), P(OEt)(3), and P(OMe)(3)), is reported. The complexes are readily synthesized from commercially available [RuCl2(3-phenylinden-1-ylidene)-(pyridine)(SIMes)] (Ind-III) in yields of up to 88%. These complexes adopt an unusual cis configuration between the phosphite and the NHC ligands. NMR experiments and computational studies confirm that the cis complexes are thermodynamically favored in comparison to their trans counterparts. In addition, the isomerization from trans to cis occurs via a mononuclear and non-dissociative mechanism. Among the four precatalysts, cis-Caz-1a, featuring a P((OPr)-Pr-i)(3) ligand, displays the highest activity in ring-closing metathesis and cross-metathesis transformations. Experiments at low catalyst loadings demonstrated the potential of this catalyst, allowing better conversions than with commonly used commercially available precatalysts

Carbene transition metal complexes have become a prevalent family of catalysts enabling numerous organic transformations. Their facile synthetic access is a matter of great importance. To this end, the Cu I -NHC transfer methodology has emerged as a powerful alternative presenting attractive advantages over other methods. Herein we report the remarkable ability of copper to not only transfer NHCs but also other types of carbene such as abnormal NHCs (aNHCs), cyclic (alkyl)(amino)carbenes (CAACs) and mesoionic carbenes (MICs) to various transition metal precursors.

Abstract:Two new and efficient dual catalytic procedures for the synthesis of tri-and tetra-substituted alkenes using aryl bromides and chlorides are reported. The formation of these vinyl arenes occurs independently in a one-pot relay and a one-pot cooperative procedure using well-defined Pd-NHC and Cu-NHC complexes. Mechanistic studies were performed to elucidate the key role of the solvent in each procedure as well as the formation of the key intermediate, [Cu(alkenylboron) (NHC)], allowing the transmetallation with the Pd-NHC co-catalyst in the cooperative catalysis.

Chemistry". -(BIDAL, Y. D.; LESIEUR, M.; MELAIMI, M.; NAHRA, F.; CORDES, D. B.; ATHUKORALA ARACHCHIGE, K. S.; SLAWIN, A. M. Z.; BERTRAND, G.; CAZIN*, C. S. J.; Adv. Synth. Catal. 357 (2015) 14-15, 3155-3161, http://dx.