Markovnikov Hydrosilylation of Alkenes: How an Oddity Becomes the Goal

Over the years, hydrosilylation of terminal alkenes has emerged as one of the most prominent applications of homogeneous catalysis. While most of the relevant reports concern β-selective hydrosilylation, yielding linear products which are of industrial importance, the opposite selectivity is also gaining increasing interest and sets the scene for the next challenges. Markovnikov hydrosilylation of alkenes, especially in its asymmetric variant, has become the aim of development of new catalytic systems successfully implementing base-metal complexes—one of the most prominent trends in contemporary catalysis. In this Perspective, we present the current state of this topic and the way it has been achieved, with special emphasis put on the issues still unresolved and prospective directions of development based on the trends present in the literature, but without unnecessary attention to some details of only historical significance.