Theh ighly chemoselective hydrogenation of neral affording citronellal is described. Ther eaction has been conducted with homogeneousr hodium complexes.A mong the set of ancillary diphosphane ligands tested, Xantphos was found to be superior. Ther elevant precatalyst hasb een generated from neutral metal sources such as Rh(acac)(CO) 2 or the carbon monoxide-free rhodium source Rh(acac)(cod) in the absence of anyb ase.Ahigh ac-tivity andchemoselectivity in favorofthe desired citronellal is achieved at 0.1 MPa and room temperature.U nder the same conditions,g eranial is also reduced to citronellal. Thea ddition of carbon monoxide to the hydrogen streama su sed in an industrial process is not necessary.Scheme 1. Synthesis of citronellal (2)b ythe chemoselective hydrogenation of citral isomers 1.
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