Abstract
AbstractDeveloping new asymmetric auto‐tandem catalysis processes, especially in a divergent manner, is highly attractive but extremely challenging. Presented herein is a palladium‐catalyzed auto‐tandem reaction between 2,4‐dienyl carbonates and o‐TsNH arylimines or trifluoroacetophenones that proceeds through a consecutive N‐allylation, vinylogous addition, π‐σ‐π isomerization, and another N‐allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to the construction of a broad spectrum of fused tetrahydroquinoline architectures with moderate to excellent enantioselectivity. Ligand control even enabled effective access to regiodivergent azetidine or chemodivergent β‐H elimination with fair enantioselectivity, further showing the versatility of the current auto‐tandem catalysis.
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