The syntheses of cycloruthenated compounds by several methods, and especially by the C-H activation pathway, have been reviewed. Many ruthenium-containing starting materials lead to these interesting organometallic compounds, which have found various applications in different fields of chemistry. Their reactivity highlights both the variety of reactions that were found to occur at the Ru-C bonds as well as the inertness of the organometallic moiety when these species are exposed to strongly oxidizing molecules or to reactive halogenation reagents. Their use as catalyst precursors showed them to be particularly efficient for hydrogenation reactions, either by H 2 or by hydride transfer.
[reaction: see text] Ruthenacycles obtained by cyclometalation of enantiopure aromatic primary or secondary amines with [(eta6-benzene)RuCl2]2 or with [(eta6-p-cymene)RuCl2]2 are efficient catalysts for asymmetric transfer hydrogenation (TOF up to 190 h(-1) at room temperature). Enantioselectivities in the transfer hydrogenation of acetophenone ranged from 38% to 89%. It is possible to prepare the catalysts in situ, which allows the use of high throughput experimentation.
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