Redox-Adaptive Auto-Tandem Catalysis: Ce(III)/Ce(IV) Interconversion-Mediated Integration of Nazarov Cyclization and Oxidative Hydroxylation

Tandem catalysis combines multiple chemical transformations into a single reaction sequence, offering significant advantages. However, tandem catalysis using a single catalyst remains challenging. We introduce a redox-adaptive strategy for autotandem catalysis employing a single homogeneous cerium catalyst to achieve the one-pot synthesis of α-hydroxylated cyclopentenones under mild aerobic conditions. The step-economical process integrates Ce(III)-mediated Nazarov cyclization with Ce(IV)-mediated oxidative hydroxylation through autonomous redox interconversion. The redox-adaptive behavior of cerium facilitates efficient transitions between distinct ionic and radical mechanisms. The obtained multifunctional products enable further skeletal modifications, demonstrating the utility of the proposed method for synthesizing complex molecular structures.