Migratory Insertion Strategies for Dearomatization

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

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