Transfer Hydrosilylation

Transfer hydrogenation is without question a common technology in industry and academia. Unlike its countless varieties, conceptually related transfer hydrosilylations had essentially been unreported until the recent development of a radical and an ionic variant. The new methods are both based on a silicon‐substituted cyclohexa‐1,4‐diene and hinge on the aromatization of the corresponding cyclohexadienyl radical and cation intermediates, respectively, concomitant with homo‐ or heterolytic fission of the SiC bond. Both the radical and ionic transfer hydrosilylation are brought into context with one other in this Minireview, and early insight into the possibility of transfer hydrosilylation is included. Although the current state‐of‐the‐art is certainly still limited, the recent advances have already revealed the promising potential of transfer hydrosilylation.