European Research Council

The distant and selective activation of unreactive C−H and C−C bonds is one of important challenges in organic chemistry. In recent years, the development of remote functionalization has received a growing interest as it allows for the activation of rather challenging C−H and C−C bonds distant from the initiation point by means of a “metal-walk.

C–H functionalization has represented a paradigm shift from the standard logic of organic synthesis. Instead of focusing on orchestration of selective reactions at functional groups, C-H activation reactions have relied on the controlled functionalization of specific C–H bonds, even in the presence of more reactive functional groups.

Despite decades of research, carbocations exhibit unpredictable reactivity, making the controlled creation of stereocenters particularly difficult.

Our primary goal is to achieve comprehensive stereocontrol over non-classical carbocations by identifying the specific substitution pattern necessary to generate these carbocations as a single isomer. Then, we will focus on precisely controlling their reactivity to form stereodefined adjacent C–X and C–C bonds at distant positions from the initial carbocation, through molecular rearrangement. This approach not only aims to tame the unpredictable nature of non-classical carbocations but also to harness their reactivities to create highly complex and defined acyclic molecular structures.