Abstract
Dual transition-metal catalysis has been introduced as a robust tool to synthesize
a diverse range of organic compounds that cannot to be accessed by traditional single-metal
catalysis. In this context, we have recently developed cooperative Rh(II)/Pd(0) dual
catalytic systems that have been utilized for the preparation of heterocyclic compounds
through the reaction between Rh(II)-carbenoid and π-allyl Pd(II)-complex intermediates
in either synergistic or tandem relay catalysis. In synergistic Rh(II)/Pd(0) dual
catalysis, the two reactive intermediates are generated simultaneously, which then
undergo formal [6+3] dipolar cycloaddition to afford medium-sized heterocyclic compounds.
On the other hand, tandem relay dual catalysis can be enabled through judicious choice
of reaction parameters, which proceed through the insertion of Rh(II)-carbenoid into
O–H or C–H bonds, followed by Pd(0)-catalyzed allylation to provide allylated benzo-fused
cyclic compounds or chiral β-lactam derivatives.
1 Introduction
2 Synergistic Dual Rh(II)/Pd(0)-Catalyzed Dipolar [6+3]-Cycloaddition for the Synthesis
of 1,4-Oxazonines
3 Tandem Relay Dual Rh(II)/Pd(0) Catalysis for the Synthesis of 2-Aminoindanones
4 Asymmetric Tandem Relay Dual Rh(II)/Pd(0) Catalysis for the Synthesis of α-Quaternary
Chiral β-Lactams
5 Tandem Relay Dual Rh(II)/Pd(0) Catalysis for the Synthesis of α-Quaternary Indolinones
and Benzofuranones
6 Conclusion
Key words
rhodium catalysis - palladium catalysis - dual catalysis - synergistic catalysis -
tandem relay catalysis - carbocycle - heterocycle