Preparation of imine complexes of ruthenium and osmium stabilised by [MCl(η 6-p-cymene)(PR3)]+ fragments

Characterization and Utility of N‐Unsubstituted Imines Synthesized from Alkyl Azides by Ruthenium Catalysis

“…Moreover, the isolated Ru-H species B effectively catalyzed the formation of the N-substituted imine 27 from benzyl azide [Eq. (16)]. Notably, the fluorescent light was not necessary in this case.…”

“…In fact, stoichiometric formation of a metal/imine complex based upon this concept has already been reported. [15][16][17][18] However, attempts using photolytic [19] or metal-catalyzed conditions [20] could not deliver the free Nunsubstituted imines, presumably because of the instability and the high reactivity of the imines. Recently, we reported a simple synthesis of an isolable bridged diruthenium complex 1 and its utility under photolytic conditions for the racemization of secondary alcohols [21] and the chemoselective hydrosilylation of aldehydes.…”

Easy Ruthenium‐Catalysed Oxidation of Primary Amines to Nitriles under Oxidant‐Free Conditions

“…The same result was obtained starting with the [Ru(p-cym)Cl 2 ] 2 precursor.I ne ach case, the characteristicN ÀHa nd CÀHs ignals, around 9-8 ppm, for the coordinated aldimine intermediate has never been observed. [26] We suggest that the coordination of the amine is directly followed by the loss of H 2 to afford an aldimine intermediate, which remains bound to the ruthenium centre. This speciesp resumably undergoes af ast dehydrogenation reaction to afford aR u-nitrile adduct.…”

In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis

“…Unsurprisingly, there have been few examples of obtaining N-unsubstituted imines directly from azides. Recently, Albertin et al (29,30) reported the preparations of metal/ imine complexes from benzyl azides (Fig. 1B).…”