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A wide variety of substrates, such as aromatic, aliphatic, and heterocyclic alcohols or carbonyl compounds, can be converted into the desired products, under anaerobic conditions, in moderate to excellent yields and without the need for additives such as bases. A larger scale, solvent\u2010free reaction is also demonstrated: the isomerization of 1\u2010octen\u20103\u2010ol with a substrate\/catalyst ratio of 20\u2009000\/1 shows a very high turnover frequency (TOF) of 18\u2009400 h<jats:sup>\u22121<\/jats:sup>, with a turnover number (TON) that reaches 17\u2009200. The catalysis for these reactions is intrinsically heterogeneous in nature, and the Ru(OH)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>\/Al<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> recovered after the reactions can be reused without appreciable loss of catalytic performance. The reaction mechanism of the present Ru(OH)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>\/Al<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>\u2010catalyzed hydrogen\u2010transfer reactions were examined with monodeuterated substrates. After the racemization of (<jats:italic>S<\/jats:italic>)\u20101\u2010deuterio\u20101\u2010phenylethanol in the presence of acetophenone was complete, the deuterium content at the \u03b1\u2010position of the corresponding racemic alcohol was 91\u2009%, whereas no deuterium was incorporated into the \u03b1\u2010position during the racemization of (<jats:italic>S<\/jats:italic>)\u20101\u2010phenylethanol\u2010OD. These results show that direct carbon\u2010to\u2010carbon hydrogen transfer occurs via a metal monohydride for the racemization of chiral secondary alcohols and reduction of carbonyl compounds to alcohols. For the isomerization, the \u03b1\u2010deuterium of 3\u2010deuterio\u20101\u2010octen\u20103\u2010ol was selectively relocated at the \u03b2\u2010position of the corresponding ketones (99\u2009% D at the \u03b2\u2010position), suggesting the involvement of a 1,4\u2010addition of ruthenium monohydride species to the \u03b1,\u03b2\u2010unsaturated ketone intermediate. The ruthenium monohydride species and the \u03b1,\u03b2\u2010unsaturated ketone would be formed through alcoholate formation\/\u03b2\u2010elimination. Kinetic studies and kinetic isotope effects show that the Ru\uf8ffH bond cleavage (hydride transfer) is included in the rate\u2010determining step.<\/jats:p>","DOI":"10.1002\/chem.200500539","type":"journal-article","created":{"date-parts":[[2005,8,10]],"date-time":"2005-08-10T04:17:15Z","timestamp":1123647435000},"page":"6574-6582","source":"Crossref","is-referenced-by-count":77,"title":["Synthetic Scope and Mechanistic Studies of Ru(OH)<sub><i>x<\/i><\/sub>\/Al<sub>2<\/sub>O<sub>3<\/sub>\u2010Catalyzed Heterogeneous Hydrogen\u2010Transfer Reactions"],"prefix":"10.1002","volume":"11","author":[{"given":"Kazuya","family":"Yamaguchi","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takeshi","family":"Koike","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miyuki","family":"Kotani","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mitsunori","family":"Matsushita","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Satoshi","family":"Shinachi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Noritaka","family":"Mizuno","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2005,10,26]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","volume-title":"Chirotechnology, Industrial Synthesis of Optically Active Compounds","author":"Sheldon R. 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See reference [2b]."},{"key":"e_1_2_6_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001325i"},{"key":"e_1_2_6_69_2","unstructured":"Ikariya and co\u2010workers have reported an efficient homogeneous racemization using [Cp*RuCl(cod)] as the catalyst. In the presence of Ph2P(CH2)2NH2and KOtBu as base the turnover frequency for the racemization of (R)\u20101\u2009areached 479 h\u22121. See reference [4l]."},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar9700163"},{"key":"e_1_2_6_71_2","unstructured":"The reduction of1\u2009bin methanol ethanol and 2\u2010propanol was carried out under the conditions of Table 3 and gave the corresponding alcohol1\u2009ain 1 5 and 93\u2009% yield respectively."},{"key":"e_1_2_6_72_2","unstructured":"The catalytic activity and selectivity for this isomerization were compared for various catalysts in the absence of bases using18\u2009aas a model substrate. The effect of solvents was also examined. See Table S1 in the Supporting information."},{"key":"e_1_2_6_73_2","unstructured":"It has been reported that the reactivity of internal allylic alcohols decreases with an increase in the steric constraints of the catalysts because the steric hindrance around the double bond of internal allylic alcohols imposes a steric barrier to coordination to the metal center(s). See reference [8]."},{"key":"e_1_2_6_74_2","unstructured":"We confirmed that no reaction proceeded under the same reaction conditions without the Ru(OH)x\/Al2O3catalyst."},{"key":"e_1_2_6_75_2","unstructured":"\u00a0"},{"key":"e_1_2_6_76_2","first-page":"290","volume":"25","author":"Molton W. N.","year":"1960","journal-title":"J. Org. Chem."},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01030a031"},{"key":"e_1_2_6_78_2","unstructured":"A kinetic isotope effect (kH\/kD) of 5.3 was observed for the reduction of1\u2009bin 2\u2010propanol and 2\u2010deuterio\u20102\u2010propanol."},{"key":"e_1_2_6_79_2","volume-title":"Chemical Kinetics, The Study of Reaction Rates in Solution","author":"Connors K. A.","year":"1990"},{"key":"e_1_2_6_80_2","unstructured":"In the reaction of a 1:1 mixture of the two allylic alcohols25\u2009aand17\u2009awith Ru(OH)x\/Al2O3 an equimolar mixture of ketones18\u2009b 25\u2009b 17\u2009b and27\u2009bwas obtained [Eq. (9)] thus showing the intermolecularity of the present hydrogen transfer."},{"key":"e_1_2_6_81_2","unstructured":"For a related 1 4\u2010addition of ruthenium species to \u03b1 \u03b2\u2010unsaturated ketones see:"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00361a018"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja043782v"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja035435b"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2003.12.002"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2004.12.026"},{"key":"e_1_2_6_87_2","unstructured":"The Arrhenius plots for the isomerization of18\u2009a(333\u2013373 K) are shown in Figure S1 in the Supporting Information. The following activation parameters were obtained from the line fit of the Arrhenius plots:Ea=16.5 kcal\u2009mol\u22121 \u0394${H{{{\\ne}\\hfill \\atop 363\\hfill}}}$=15.8 kcal\u2009mol\u22121 \u0394${S{{{\\ne}\\hfill \\atop 363\\hfill}}}$=\u221230.5 eu and \u0394${G{{{\\ne}\\hfill \\atop 363\\hfill}}}$=26.8 kcal\u2009mol\u22121."},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9905524"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29900001651"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo971046m"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200500539","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200500539","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T22:17:36Z","timestamp":1760307456000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200500539"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2005,10,26]]},"references-count":95,"journal-issue":{"issue":"22","published-print":{"date-parts":[[2005,11,4]]}},"alternative-id":["10.1002\/chem.200500539"],"URL":"https:\/\/doi.org\/10.1002\/chem.200500539","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2005,10,26]]}}}