{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T08:03:39Z","timestamp":1789459419151,"version":"build-2803163510"},"reference-count":82,"publisher":"Wiley","issue":"1-2","license":[{"start":{"date-parts":[[2006,7,3]],"date-time":"2006-07-03T00:00:00Z","timestamp":1151884800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2006,7,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Chiral arene\u2013<jats:italic>N<\/jats:italic>\u2010tosylethylenediamine\u2013Ru<jats:sup>II<\/jats:sup> complexes can be made to effect both asymmetric transfer hydrogenation and asymmetric hydrogenation of simple ketones through a slight functional modification and by switching reaction conditions. [Ru(OSO<jats:sub>2<\/jats:sub>CF<jats:sub>3<\/jats:sub>){(<jats:italic>S,S<\/jats:italic>)\u2010TsNCH(C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>)CH(C<jats:sub>6<\/jats:sub>H<jats:sub>5<\/jats:sub>)NH<jats:sub>2<\/jats:sub>}(\u03b7<jats:sup>6<\/jats:sup>\u2010<jats:italic>p<\/jats:italic>\u2010cymene)] catalyzes the asymmetric hydrogenation of acetophenone in methanol to afford (<jats:italic>S<\/jats:italic>)\u20101\u2010phenylethanol with 96\u2009%\u2005<jats:italic>ee<\/jats:italic> in 100\u2009% yield. Like the transfer hydrogenation catalyzed by similar Ru catalysts with basic 2\u2010propanol or a formic acid\/triethylamine mixture, this hydrogenation proceeds through a metal\u2013ligand bifunctional mechanism. The reduction of the C\uf8feO function occurs via an intermediary 18e RuH species in its outer coordination sphere without metal\u2013substrate interaction. The high catalytic efficiency relies on the facile ionization of the Ru triflate complex in methanol. The turnover rate is dependent on hydrogen pressure and medium acidity and basicity. The RuCl analogue can be used as a precatalyst, albeit less effectively. Unlike the well\u2010known diphosphine\u20131,2\u2010diamine\u2013Ru<jats:sup>II<\/jats:sup>\u2010catalyzed hydrogenation that proceeds in a basic alcohol, this reaction takes place under slightly acidic conditions, creating new opportunities for asymmetric hydrogenation.<\/jats:p>","DOI":"10.1002\/asia.200600098","type":"journal-article","created":{"date-parts":[[2006,7,5]],"date-time":"2006-07-05T16:47:33Z","timestamp":1152118053000},"page":"102-110","source":"Crossref","is-referenced-by-count":164,"title":["Mechanism of Asymmetric Hydrogenation of Acetophenone Catalyzed by Chiral \u03b7<sup>6<\/sup>\u2010Arene\u2013<i>N<\/i>\u2010Tosylethylenediamine\u2013Ruthenium(II) Complexes"],"prefix":"10.1002","volume":"1","author":[{"given":"Christian\u2005A.","family":"Sandoval","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takeshi","family":"Ohkuma","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Noriyuki","family":"Utsumi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kunihiko","family":"Tsutsumi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kunihiko","family":"Murata","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryoji","family":"Noyori","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2006,7,10]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/b502713f"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","volume-title":"Comprehensive Asymmetric Catalysis, Vol. 1","author":"Ohkuma T.","year":"1999"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/0471721506.ch1"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200390000"},{"key":"e_1_2_6_6_2","first-page":"25","volume-title":"Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals, Vol. 2","author":"Ohkuma T.","year":"1998"},{"key":"e_1_2_6_7_2","unstructured":"For reviews on the mechanism of AH see:"},{"key":"e_1_2_6_8_2","volume-title":"Asymmetric Catalysis in Organic Synthesis","author":"Noyori R.","year":"1994"},{"key":"e_1_2_6_9_2","volume-title":"Asymmetric Synthesis, Vol. 5","author":"Halpern J.","year":"1994"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.07.018"},{"key":"e_1_2_6_11_2","volume-title":"Mechanisms in Homogeneous 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complexes effect AH and ATH of unsaturated carboxylic acids:"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00390a043"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(00)82111-4"},{"key":"e_1_2_6_37_2","unstructured":"Achiral (cyclopentadienone)Ru\u2013carbonyl complexes effect hydrogenation and transfer hydrogenation (2\u2010propanol with KOH) of acetophenone:"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00127a027"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002177z"},{"key":"e_1_2_6_40_2","unstructured":"[Ru(Diphosphine)(\u03b1\u2010picolylamine)Cl2] complexes catalyze both hydrogenation and transfer hydrogenation depending on the phosphine ligands under basic conditions:"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja052071"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0491701"},{"key":"e_1_2_6_43_2","unstructured":"T. Ohkuma N. Utsumi K. Tsutsumi K. Murata C.\u2005A. Sandoval R. Noyori J. Am. Chem. Soc.in press."},{"key":"e_1_2_6_44_2","unstructured":"Although AH of ketones with [RuH(\u03b71\u2010BH4)(binap)(1 2\u2010diamine)] in 2\u2010propanol takes place without extra base the medium is slightly basic owing to the reaction of the BH4\u2212anion and 2\u2010propanol:"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja026136"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja043339k"},{"key":"e_1_2_6_47_2","unstructured":"For the notation of the absolute configuration see:"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)80382-4"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00855a063"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1002\/mrc.1728"},{"key":"e_1_2_6_51_2","unstructured":"\u00a0"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60277a003"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1039\/cs9831200415"},{"key":"e_1_2_6_54_2","volume-title":"Principles and Applications of Organotransition Metal Chemistry","author":"Collman J. 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L.","year":"1983","journal-title":"Adv. Inorg. Bioinorg. Mech."},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0898-8838(08)60016-1"},{"key":"e_1_2_6_69_2","unstructured":"Under basic conditions (S S)\u20103\u2009agave (S)\u20102with the same 95\u201396\u2009%\u2005ee(see Experimental Section)."},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00002a029"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0487175"},{"key":"e_1_2_6_72_2","first-page":"427","volume-title":"Organic Chemistry","author":"Wade L. 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