ABSTRACT Heteroannular palladium migration on stacked molecules is one of the keys for achieving distal C–H activation by avoiding the template design. However, the possibility of migration is only realized when a relatively stable palladacycle is formed at a distal position with the aid of a transient directing group. Herein, we have revealed that heteroannular palladium migration facilitated by a monodentate transient directing group, along with an additional ligand, can help to fine‐tune the desired bite angle for palladium migration. The developed reaction effectively demonstrates 23 examples of distal heteroannular C–H functionalization of ferrocenecarboxaldehydes, a process that has been less extensively studied compared to the homoannular cyclopentadienyl (Cp) ring C–H activation. Furthermore, the control experiments have been performed to understand monodentate transient directing group (TDG)‐enabled heteroannular palladium migration, favored by the monodentate TDG and ligand.
Dhumale et al. (Thu,) studied this question.
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