# Synergistic solvent-catalyst paradigm for sustainable aerobic allylic C–H functionalization

## TL;DR

A new sustainable method for allylic C–H functionalization uses a synergistic Pd/hydroquinone system with ethanol/water under mild conditions, achieving high efficiency and stereocontrol.

## Contribution

The study introduces a synergistic solvent-catalyst system for sustainable allylic C–H functionalization with exceptional efficiency and pharmaceutical relevance.

## Key findings

- A Pd/hydroquinone system enables aerobic allylic C–H functionalization at room temperature with high turnover frequency.
- The method achieves over 90 products with up to 96% yield and 93% ee for quaternary stereocenters.
- The platform integrates green solvent engineering and cooperative catalysis for scalable pharmaceutical synthesis.

## Abstract

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 (room temperature to 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 products (up to 96% yield). 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 allylic functionalized molecules with pharmaceutical interests, demonstrating how molecule-level innovation can drive sustainable industrial transformation.

This study has developed a solvent-catalyst synergistic paradigm for aerobic C–H allylic functionalization reactions, illustrating a sustainable blueprint that integrates atom economy with pharmaceutical relevance.