Copper-Catalyzed Hydrofunctionalization of Alkynes

We have developed a general approach to the catalytic hydrofunctionalization of alkynes, involving hydrocupration and electrophilic functionalization of the resulting alkenylcopper intermediate. Using this approach with different electrophiles we have developed three transformations: semireduction, hydrobromination, and hydroalkylation of alkynes. In the context of a brief history of copper hydride complexes in organic chemistry, in this account we describe the key developments that inspired and enabled our research. We also describe the reaction development, the scope, and the mechanism of these transformations. In the process, we highlight some of the challenges inherent to our approach and summarize new insights that allowed us to successfully address them. 1 Introduction 2 Semireduction 3 Hydrobromination 4 Hydroalkylation 5 Conclusions