An efficient method for the rhodiumo nc arbon matrix catalyzed preparation of secondary andt ertiarya mines,c yanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds was developed, including ac onvenient procedure for the tandem formal reductiveaddition of acetonitrile to aldehydes.T he catalyst could be reused,a nd at least three consecutive reaction cycles werep erformed with comparable efficiency.T he method was shown to be compatible with functional groupsp rone to reduction by hydrogen and complex hydrides.ReductiveC ÀCa nd CÀNb ond-forming reactions are widely used as powerful and convenient tools to build up molecular complexity rapidly.[1] Whereas in the paradigm of fine laboratory synthesis classicals ynthetic approaches are being constantly improved and refined to meet ever-increasing stringency of requirements forr eactivity,s electivity and cost, we strongly believe that the academic community should pay greatera ttention to optimization of synthetic tools in terms of the integral economic ande nvironmental effects they might have if conducted on semi-industrial or industrial scale. In this context, the use of side products of the chemical industry as starting materials for novel synthetic protocols represents av ery valuable concept. Our group recently discovered catalytic reductive methodology [2] that takes advantage of the deoxygenative potential of carbon monoxide and does not requirea ne xternal hydrogen source, unlike conventionala pproaches such as reductive amination and reductive Knoevenagel condensation. As carbon monoxide is produced in multiton quantities as as ide product of steelmaking, [3] it represents an abundant source for chemical synthesis and is am ore atom-economical [4] alternative to many of the established synthetic agents. Moreover,d espite the fact that certain precautions have to be taken while working with carbon monoxide because of its toxicity, its higher flammability limit relative to that of hydrogen represents an important advantage especiallyo nalarger reaction scale.[5] Whereas the use of CO has been systematically investigated in the reduction of, for example, aromatic nitro groups, [6,7] its potentiala sareductivea gent still remains considerably underexplored.Heterogeneous catalysis is oftentimes much more convenient with respect to homogeneous alternatives, for example, in terms of catalyst recovery andp urificationo ft he products; [8] and the intrinsic merits of heterogeneous catalytic systems are, therefore, responsible forw ide applications thereof in nearly all areas of chemical industry owing to the improved economic and environmental profiles. Given that our growing toolboxo f methodse mploying CO as ad eoxygenative agent have so far involved homogeneous protocols, [2] we were particularly interested in the development of ah eterogeneous system of comparable potentialthat would render our method more compatible with the generalr equirements of industrial-scale production. Thus, herein we report an atom-economical heter...

A ruthenium-catalyzed reductive amination without an external hydrogen source has been developed using carbon monoxide as the reductant and ruthenium(III) chloride (0.008-2 mol %) as the catalyst. The method was applied to the synthesis of antianxiety agent ladasten.

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