Iridium-Catalyzed Acid-Assisted Hydrogenation of Oximes to Hydroxylamines

We found that cyclometalated cyclopentadienyl iridium(III) complexes are uniquely efficient catalysts in homogeneous hydrogenation of oximes to hydroxylamine products. A stable iridium C,N-chelation is crucial, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. Several Ir-complexes were mapped by X-ray crystal analysis in order to collect steric parameters that might guide a rational design of even more active catalysts. A broad range of oximes and oxime ethers were activated with stoichiometric amounts of methanesulfonic acid and reduced at room temperature, remarkably without cleavage of the fragile N-O bond. The exquisite functional group compatibility of our hydrogenation system was further demonstrated by additive tests. Experimental mechanistic investigations support an ionic hydrogenation platform, and suggest a role for the Bronsted acid beyond a proton source. Our studies provide deep understanding of this novel acidic hydrogenation and may facilitate its improvement and application to other challenging substrates.

Automated summary

Cyclometalated cyclopentadienyl iridium(III) complexes are efficient catalysts in the hydrogenation of oximes, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. The stable iridium C,N-chelation is crucial for the catalytic activity, and the hydrogenation system demonstrates high functional group compatibility.