Dedicated to the memory of Prof. Dieter Enders
Abstract
Development of strategies for molecule functionalization by dearomatization has surged
in the last two decades. The benefits of overcoming the resonance stabilization energy
outweigh the cost; diverse compounds could be accessed in a short number of steps.
One approach that has been of interest in recent years is the dearomatization of indoles
and other (hetero)aromatic compounds by migratory insertion. The chiral σ-bond palladium
intermediate could be reduced or trapped by a second functionalization. In this short
review we will summarize the recently discovered reactions from our group and others
in this field of metal-catalyzed dearomatizations by migratory insertion.
1 Introduction
2 Monofunctionalizations: Heck and Reductive Heck Reactions
2.1 N-Tethered Heterocycles
2.2 Non-N-tethered Heterocycles
2.3 Non-heterocycles
3 Dearomative Difunctionalizations: Interrupted Heck Reaction
3.1 N-Tethered Heterocycles
3.2 Non-N-tethered Heterocycles
4 Conclusion
Key words
palladium - nickel - dearomatization - migratory insertion - carbopalladation - difunctionalization