Iridium-Catalyzed Highly Selective 1,4-Reduction of α,β-Unsaturated Carbonyl Compounds.

In this study, an iridium-catalyzed selective 1,4-reduction of α,β-unsaturated carbonyl compounds is realized, with water as a solvent and formic acid as a hydride donor. The new efficient iridium catalyst features a 2-(4,5-dihydroimidazol-2-yl)quinoline ligand. The chemoselectivity and catalyst efficiency are highly dependent on the electronic and steric properties of the substrates. For α,β-unsaturated amides, acids, and esters, only the electron-deficient C=C bonds are reduced (1,4-reduction), and the other functional groups are left intact. The ratio and initial TOF reach 7000 and 18,480 h, respectively. A gram-scale 1,4-reduction is also performed. Deuterium labeling shows that the β-hydrogens of the products originate from the formyl hydrogen in the formic acid. The application of the 1,4-reduction for the modification the structures of some medications is demonstrated.