BIAN-Aluminium-Catalysed Imine Hydrogenation.

Hydrogenations have been dominated by transition metal catalysis, while the use of more abundant and inexpensive main group metal catalysts has remained a great challenge. Here, a bimetallic Li/Al dihydride was successfully applied to catalytic hydrogenations of imines. The catalyst [(DippBIAN)Al(µ-H)2Li(OEt2)2] was easily prepared from the 2e-reduced BIAN derivative and LiAlH4.

Redox-active BIAN-based Diimine Ligands in Metal-Catalyzed Small Molecule Syntheses.

α-Diimine ligands have significantly shaped the coordination chemistry of most transition metal complexes. Among them, bis(imino)acenaphthene ligands (BIANs) have recently been matured to great versatility and applicability to catalytic reactions. Besides variations of the ligand periphery, the great versatility of BIAN ligands resides within their ability to undergo facile electronic manipulations. This review highlights key aspects of BIAN ligands in metal complexes and summarizes recent contributions of metal-BIAN catalysts to syntheses of small and functionalized organic molecules.

Iron-catalysed allylation-hydrogenation sequences as masked alkyl-alkyl cross-couplings.

An iron-catalysed allylation of organomagnesium reagents (alkyl, aryl) with simple allyl acetates proceeds under mild conditions (Fe(OAc)2 or Fe(acac)2, Et2O, r.t.) to furnish various alkene and styrene derivatives. Mechanistic studies indicate the operation of a homotopic catalyst. The sequential combination of such iron-catalysed allylation with an iron-catalysed hydrogenation results in overall C(sp3)-C(sp3)-bond formation that constitutes an attractive alternative to challenging direct cross-coupling protocols with alkyl halides.