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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

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Formal Deoxygenative Hydrogenation of Lactams Using PN^HP-Pincer Ruthenium Complexes under Nonacidic Conditions

Osamu Ogata¹, Hideki Nara¹, Kazuhiko Matsumura¹

¹Corporate Research and Development Division , Takasago International Corporation , 1-4-11 Nishi-Yawata , Hiratsuka , Kanagawa 254-0073 , Japan.

Organic Letters

|December 7, 2019

Abstract:

A formal deoxygenative hydrogenation of amides to amines with RuCl₂(NHC)(PN^HP) (NHC = 1,3-dimethylimizadol-2-ylidene, PN^HP = bis(2-diphenylphosphinoethyl)amine) is described. Various secondary amides, especially NH-lactams, are reduced with H₂ (3.0-5.0 MPa) to amines at a temperature range of 120-150 °C with 1.0-2.0 mol % of PN^HP-Ru catalysts in the presence of Cs₂CO₃. This process consists of (1) deaminative hydrogenation of secondary amides to generate primary amines and alcohols, (2) dehydrogenative coupling of the transient amines with alcohols to generate imines, and (3) hydrogenation of imines to give the formally deoxygenated secondary amine products.

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