Abstract
Carbocations have played a central role in the chemical sciences for over a century.
In a synthetic setting, most methods utilize stabilized tricoordinate carbocations,
while there are far fewer examples of reactions featuring nonstabilized dicoordinate
cations. Here, we provide an overview of recent developments in the generation of
high-energy carbocations mediated by weakly coordinating anions and the C–H insertion
reactions of such carbocations. Moreover, we discuss mechanistic studies of these
catalytic C–H insertion reactions aimed at furthering our understanding of the reactive
nature of these rarely invoked cationic intermediates.
1 Introduction
2 Background: Phenyl Carbocations
3 Silylium/Carborane-Catalyzed C–H Insertion Reactions of Phenyl Carbocations
4 Silane-Fueled, Weakly Coordinating Anion-Catalyzed, Reductive C–H Insertion Reactions
of Vinyl Carbocations
5 C–H Insertion Reactivity of Vinyl Carbocations under Basic Conditions
6 Conclusion and Outlook
Key words
carbocations - weakly coordinating anions - C–H insertion reactions - catalysis -
C–H functionalization - organocatalysis
