Kinetic and Mechanistic Studies of the Selective Hydrogenation of ( <i>E</i> )‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh ₃ Complexes

γ-Valerolactone as a renewable, polar aprotic solvent was evaluated in the selective hydrogenation of carbon-carbon double bond chalcones from both catalytic and mechanistic aspects. By using triphenylphosphine-modified cationic rhodium catalyst systems reasonably high activities (TOFinitial∼1200 h−1) were achieved (E)-chalcone (CHL), common model substrate for α,β-unsaturated ketones, to dihydrochalcone (DHC). Various derivatives CHL, which substituted on styryl phenyl groups also showed exclusive selectivity C=C bond. The optimal PPh3/Rh ratio between 2.5 3, but higher ratios advantageously tolerated, is beneficial process chemistry. GVL proved stable enough under reaction conditions waste-free recycling. Kinetic studies NMR spectra analogous deuteration chalcone by Rh-PPh3 system clearly show olefin insertion rate-determining step with definite irreversibility. investigating substituent effect ring moiety chalcone, quasi-linear correlation found electronic parameters para-substituents activity electron donor being favorable rate. In summary, an environmentally friendly feasible method presented production valuable DHC intermediates view their pharmaceutical importance.