This work demonstrates that ligand effects influence regioselectivity in Pd-catalyzed allylation of arylamines, implying distinct pathway modulations depending on the ligand used.
-fused product, whereas the bulky WingPhos ligand reverses the diastereoselectivity by stabilizing an alternative vinylogous addition transition state through steric confinement and favorable noncovalent interactions within a well-defined chiral pocket. In contrast, the BINOL-derived phosphoramidite ligand alters the relative energetics of competing N-allylation pathways, favoring a distinct regioselective N-allylation that leads to azetidine formation. The ligand-dependent steric effects, dispersion interactions, and electronic factors collectively differentiate the competing pathways, thereby clarifying how distinct chiral ligand environments modulate pathway selection in this Pd-catalyzed cascade reaction.
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Zhao et al. (2026) studied this question.
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