Mechanistic Complexity of Asymmetric Transfer Hydrogenation with Simple Mn-Diamine Catalysts
Robbert Van Putten (TU Delft - Applied Sciences)
Georgy A. Filonenko (TU Delft - Applied Sciences)
Angela Gonzalez De Castro (InnoSyn B.V., Geleen)
Chong Liu (TU Delft - Applied Sciences)
Manuela Weber (Freie Universität Berlin)
Christian Müller (Freie Universität Berlin)
Laurent Lefort (InnoSyn B.V., Geleen)
Evgeny Pidko (ITMO University, TU Delft - Applied Sciences, TU Delft - ChemE/Algemeen)
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Abstract
The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.
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