of Chemistry, Massachusetts Institute of Technology,
Cambridge, Massachusetts, USA
"Nickel-catalyzed coupling reactions: development and application"
The development and use of several nickel-catalyzed
carbon-carbon bond-forming reactions will be discussed.Ê Conceptually,
these transformations enhance the nucleophilicity of
a ¹-bond in an alkyne, allene, or alkene, such that it reacts with an electrophile (such as an aldehyde, ketone, epoxide, imine).Ê The transformations are selective in many respects and are also tolerant of a wide range of functional groups.Ê For these reasons, and because the products of the coupling reactions are found in many families of structurally complex natural products, the nickel-catalyzed methods have been used as fragment coupling methods for the union of late-stage, highly functionalized intermediates in total synthesis. Ê Several examples of the interrelationships of methods development and target-oriented synthesis will be presented.