Innovative synergistic solvent-catalyst paradigm for sustainable allylic C–H functionalization

Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C–H functions under ambient conditions (rt–50 °C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 substrates (up to 99% yield), directly aligning with China’s strategic goals for decarbonizing chemical manufacturing. It also delivers exceptional stereocontrol (up to 93% ee for quaternary stereocenters) and enables advanced allylic transformations within a green framework through additional synergistic catalysis. By integrating solvent engineering with cooperative catalysis, we have developed a scalable platform for the synthesis of FDA-certified allylic pharmaceuticals and high-value chemicals. demonstrating how molecular-level innovation can drive sustainable industrial transformation.