Selective Base‐free Transfer Hydrogenation of α,β‐Unsaturated Carbonyl Compounds using iPrOH or EtOH as Hydrogen Source

Publisher： John Wiley & Sons Inc

E-ISSN： 1521-3765|24|11|2725-2734

ISSN： 0947-6539

Source： CHEMISTRY - A EUROPEAN JOURNAL, Vol.24, Iss.11, 2018-02, pp. : 2725-2734

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Abstract

AbstractCommercially available Ru‐MACHOTM‐BH is an active catalyst for the hydrogenation of several functional groups and for the dehydrogenation of alcohols. Herein, we report on the new application of this catalyst to the base‐free transfer hydrogenation of carbonyl compounds. Ru‐MACHOTM‐BH proved to be highly active and selective in this transformation, even with α,β‐unsaturated carbonyl compounds as substrates. The corresponding aliphatic, aromatic and allylic alcohols were obtained in excellent yields with catalyst loadings as low as 0.1–0.5 mol % at mild temperatures after very short reaction times. This protocol tolerates iPrOH and EtOH as hydrogen sources. Additionally, scale up to multi‐gram amounts was performed without any loss of activity or selectivity. An outer‐sphere mechanism has been proposed and the computed kinetics and thermodynamics of crotonaldehyde and 1‐phenyl‐but‐2‐en‐one are in perfect agreement with the experiment.

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