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The AH and ATH catalytic cycles are linked by the metal\u2013ligand bifunctional mechanism. Asymmetric reduction of pinacolone is best achieved in ethanol containing the Ru catalyst and base under an H<jats:sub>2<\/jats:sub> atmosphere at ambient temperature, giving the chiral alcohol in 97\u201398\u2009%\u2005<jats:italic>ee<\/jats:italic>. The reaction utilizes only H<jats:sub>2<\/jats:sub> as a hydride source with alcohol acting as a proton source. On the other hand, asymmetric reduction of acetophenone is attained with both H<jats:sub>2<\/jats:sub> (ambient temperature) and 2\u2010propanol (&gt;60\u2009\u00b0C) with relatively low enantioselectivity. The degree of contribution of the AH and ATH cycles is highly dependent on the ketone substrates, solvent, and reaction parameters (H<jats:sub>2<\/jats:sub> pressure, temperature, basicity, substrate concentration, H\/D difference, etc.).<\/jats:p>","DOI":"10.1002\/asia.200800246","type":"journal-article","created":{"date-parts":[[2008,9,15]],"date-time":"2008-09-15T08:56:02Z","timestamp":1221468962000},"page":"1801-1810","source":"Crossref","is-referenced-by-count":66,"title":["The Hydrogenation\/Transfer Hydrogenation Network in Asymmetric Reduction of Ketones Catalyzed by [RuCl<sub>2<\/sub>(binap)(pica)] 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