First Titanium-Catalyzed anti-1,4-Hydrosilylation of Dienes

1,4-Hydrosilylation of dienes catalyzed by late transition metals constitutes a straightforward access to allylsilanes. However, when unsymmetric dienes are used, it generally leads to a mixture of regioisomers (tail or head products) via Z -specific 1,4-addition. Here we describe the first catalytic anti -1,4-hydrosilylation of dienes using the cheap and stable Cp 2 TiF 2 complex as catalyst. It affords E -allylsilanes in good to excellent yields with an unprecedented regio- and diastereoselectivity. Dehydrogenative double silylation of dienes can be selectively obtained by simply changing the activation protocol of the precatalyst.