This Review examines recent developments in late transition metal-catalyzed hydroamination and-amidation reactions. A hydroamination is a reaction in which an N− H unit of a nucleophilic primary/secondary amine or ammonia is added across a C− C multiple bond with cleavage of the N− H bond and formation of a C− N and a C− H bond. Acyl, sulfonyl, or phosphinyl substituents acidify the N− H proton by 5− 20 orders of magnitude and markedly reduce the nucleophilicity of the nitrogen. 1 These strongly electron-withdrawing substituents fundamentally alter the reactivity of the N− H group, so that different product classes are obtained in catalytic addition reactions of amine-and amide-type substrates. Although the addition of amides and related compounds across C− C multiple bonds is sometimes also called hydroamination, such reactions appear to be more accurately designated as hydroamidations, because of the differences in substrates, reactivity, and products. In this Review, usage of the term hydroamidation is not limited to the substrate classes of amides, sulfonamides, and phosphonamides, but extended to structurally related compounds with a similar pKa range and reactivity, such as carbamates, lactams, ureas, amidines, guanidines, etc. 1.1. Products Obtainable by Hydroaminations and Hydroamidations

Amine, enamine/imine, or enamide moieties, as are accessible by hydroamination or-amidation reactions, are widely encountered in the scaffolds of natural products or synthetic drugs (Figure 1). Monomorine is one of the first natural products that became accessible by a synthetic sequence involving a hydroamination step. 2