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Catalysts containing thioamide ligands derived from <jats:sc>L<\/jats:sc>\u2010valine were found to selectively generate the product with an <jats:italic>R<\/jats:italic> configuration (95\u2009% <jats:italic>ee<\/jats:italic>), whereas the corresponding <jats:sc>L<\/jats:sc>\u2010valine\u2010based hydroxamic acids or hydrazides facilitated the formation of the (<jats:italic>S<\/jats:italic>)<jats:italic>\u2010<\/jats:italic>alcohols (97 and 91\u2009% <jats:italic>ee<\/jats:italic>, respectively). The catalytic reduction was examined by performing a structure\u2013activity correlation investigation with differently functionalized or substituted ligands and the results obtained indicate that the major difference between the thioamide and hydroxamic acid based catalysts is the coordination mode of the ligands. Kinetic experiments were performed and the rate constants for the reduction reactions were determined by using rhodium\u2013arene catalysts derived from amino acid thioamide and hydroxamic acid ligands. The data obtained show that the thioamide\u2010based catalyst systems demonstrate a pseudo\u2010first\u2010order dependence on the substrate, whereas pseudo\u2010zero\u2010order dependence was observed for the hydroxamic acid containing catalysts. Furthermore, the kinetic experiments revealed that the rate\u2010limiting steps of the two catalytic systems differ. From the data obtained in the structure\u2013activity correlation investigation and along with the kinetic investigation it was concluded that the enantioswitchable nature of the catalysts studied originates from different ligand coordination, which affects the rate\u2010limiting step of the catalytic reduction reaction.<\/jats:p>","DOI":"10.1002\/chem.200900548","type":"journal-article","created":{"date-parts":[[2009,9,11]],"date-time":"2009-09-11T13:48:18Z","timestamp":1252676898000},"page":"11197-11209","source":"Crossref","is-referenced-by-count":56,"title":["Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Amino Acid Derived Rhodium Complexes: On the Origin of Enantioselectivity and Enantioswitchability"],"prefix":"10.1002","volume":"15","author":[{"given":"Katrin","family":"Ahlford","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jesper","family":"Ekstr\u00f6m","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexey\u2005B.","family":"Zaitsev","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Per","family":"Ryberg","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lars","family":"Eriksson","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hans","family":"Adolfsson","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,10,20]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"\u00a0"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00013a015"},{"key":"e_1_2_5_3_2","first-page":"199","volume-title":"Comprehensive Asymmetric Catalysis I\u2010III, Vol.\u20051","author":"Ohkuma T.","year":"1999"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200390000"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200390030"},{"key":"e_1_2_5_6_2","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1002\/9783527619405.ch4c","volume-title":"Transition Metals for Organic Synthesis, Vol.\u20052","author":"Gladiali S.","year":"2004"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1595\/147106705X75421"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513564H"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar9502341"},{"key":"e_1_2_5_10_2","first-page":"333","volume":"10","author":"Bianchini C.","year":"1997","journal-title":"Chemtracts"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(99)00216-5"},{"key":"e_1_2_5_12_2","first-page":"43","volume":"1","author":"Ohkuma T.","year":"2004","journal-title":"Compr. 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