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Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines†
Jose R. Cabrero-Antonino,Kathrin Junge,Henrik Junge,Matthias Beller
Chemical Science Pub Date : 02/09/2016 00:00:00 , DOI:10.1039/C5SC04671H
Abstract

A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)3. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.

Graphical abstract: Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines
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