The rhodium-catalyzed reactions of 3-diazoindolin-2-imines with N,N-dialkylanilines, N-allyl-N-alkylanilines, and N-propargyl-N-alkylanilines and 3-diazoindolin-2-imines furnished 3-aryl-2-aminoindoles, 3-allyl-3-amino-2-iminoindolines, and tetrahydro-[1,4]diazepino[2,3-b]indoles, respectively. 3-Diazoindolin-2-imines acted as precursors of α-imino rhodium carbenes in these transformations.

N-Galactosyl aziridines were synthesized via BF3·OEt2 promoted addition of carbenes generated from diazocarbonyl compounds with O-pivaloylated β-D-galactosylimines in good yields and high diastereoselectivity. The ring-opening reactions with p-toluenethiol of the aziridines provided enantiometrically pure β-S-substituted phenylalanine derivatives in a highly regioselective manner.

Herein we report robust methods for the preparation and full characterisation of a range of Ir(I) and Rh(I) fluoride and bifluoride complexes using N-heterocyclic carbenes (NHCs) as ancillary ligands. The processes that link the fluoride and the bifluoride species are investigated and reports of the first Ir-bifluoride and Ir(I)-NHC and Rh(I)-NHC trifluoromethyl complexes are revealed.

The electrochemical generation of N-heterocyclic carbenes (NHCs) offers a mild and selective alternative to traditional synthetic methods that usually rely on strong bases air-sensitive materials. use electrons as reagents results in an efficient clean synthesis enables the direct NHCs various applications. Herein, electrogenerated organocatalysis, organometallic chemistry is explored.

The effects of halogens; fluorine, chlorine and bromine, on the stability and multiplicity of phenylcarbenes / silylenes/ germylenes structures are compared and contrasted at B3LYP/6-311++G**//B3LYP/6-31+G* level. The singlet-triplet energy gaps, ΔES-T , values for all the above speciesincrease through fluorinated up, ΔES-Ts and ΔEHOMO–LUMOs support the stability of the singlet statesinspite of...

This article discusses the concept of N-heterocyclic carbenes (NHCs) equipped with more than one functional moiety, which allows using these NHCs for multiple purposes. A pioneering example for such NHCs is N-phosphine oxide-substituted imidazolylidenes (PoxIms), and their synthesis and strategic use are highlighted. The utility of PoxIms by far exceeds the conventional use as multidentate liga...

Chiral N-heterocyclic carbenes (NHCs) promote the asymmetric formal [4 + 2] cycloaddition of alkylarylketenes with β,γ-unsaturated α-ketocarboxylic esters and amides. Divergent diastereoselectivity is observed in this process, with γ-aryl-β,γ-unsaturated α-ketocarboxylic esters and amides giving preferentially syn-dihydropyranones (up to 68 : 32 dr syn : anti, up to 98% ee), while γ-alkyl-deriv...

N-heterocyclic carbenes (NHCs) represent a leading class of ligands in organometallic chemistry, but have been rarely exploited as stabilizers for metal nanoparticles (NPs). We report the first example of NHC stabilized Pd-NPs that demonstrate long term stability. These NHC Pd-NPs were synthesized by a facile ligand exchange protocol using rationally designed long chained NHCs (LC-NHCs). Furthe...