This Thesis describes the development of transition-metal-catalyzed alkene additions reactions through the activation of C--C and C--heteroatom sigma-bonds. In these transformations, a C--C or C--heteroatom sigma-bond is activated, cleaved, and added across an alkene double bond without inducing fragmentation, allowing addition of an alkene with vicinal functional groups and rapid construction of carbo- and heterocycles in an atom-economical manner. Chapter 1 provides an overview of catalytic alkene addition reactions and C--C sigma-bond activation reactions. Chapters 2, 3, and 5 describe alkene addition reactions by catalytic activation of C--CN, C--O, and N--CN sigma-bonds, respectively. An unprecedented metal-free N--CN bond cleavage process is discussed in Chapter 4. |