Bimetallic Cooperative Catalyst

Well-defined mechanism

A Rh/Cu bimetallic cooperative catalyst for C–H allylation of benzamides, with a well-established mechanism validated both experimentally and theoretically, providing a reliable model for developing efficient C–H functionalization reactions.

Li-Feng, Yao · Zhang, Lei · Fang, Decai

Organometallics 2024

Advantages

Active species identified

The complex CAT-A formed from Cp*Rh(OAc)Cl and Cu(OAc)2(DMA) is identified as the most likely active catalyst, enabling targeted design.

Ligand shuttling resolved

Cu dissociates and then returns to Rh to deliver OAc and Cl ligands, enabling catalyst regeneration and informing the design of analogous cooperative systems.

Mechanistic insight generalizable

Exploration of subsequent reactions and substituent effects provides a comprehensive explanation of experimental yields, aiding prediction and optimization of related reactions.

Applications

• C–H Functionalization：Use the mechanistic model to design new bimetallic catalytic systems, avoiding blind screening.
• Allylation：Mechanistic details help develop more efficient allylation conditions.
• Rhodium Catalysis：Clarifies key steps of oxidation state changes and ligand exchange in the Rh catalytic cycle.
• Copper Catalysis：Reveals Cu's special role as a ligand shuttle, inspiring new cooperative catalytic strategies.
• Organic Synthesis Methodology：The mechanistic framework can be transferred to other bimetallic-catalyzed C–H functionalization reactions.