Wang Rui, Zhang Long, Luo Sanzhong
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
Natl Sci Rev. 2025 May 16;12(8):nwaf196. doi: 10.1093/nsr/nwaf196. eCollection 2025 Aug.
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% 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.
实现可持续的催化转化需要对溶剂体系、催化基序和能量输入进行协同优化。在此，我们报道了一种协同的钯/对苯二酚催化体系，该体系能在环境条件（室温至50°C，空气）下，以乙醇/水作为绿色介质，通过高周转频率（TOF）实现需氧烯丙基C-H官能化。该策略实现了无与伦比的合成效率，并在涉及90多种产物（产率高达96%）的两个关键转化（烷基化和胺化）中展现出显著的通用性。它还提供了出色的立体控制（季碳立体中心高达93%），并通过额外的协同催化在绿色框架内实现了先进的烯丙基转化。通过将溶剂工程与协同催化相结合，我们开发了一个可扩展的平台，用于合成具有药物价值的烯丙基官能化分子，展示了分子层面的创新如何推动可持续的工业转型。
