Linear Hydroaminoalkylation Products from Alkyl‐Substituted Alkenes

The regioselective conversion of alkyl‐substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N‐methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one‐pot procedure that includes an initial alkene hydroaminoalkylation with an α‐silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl‐substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the α‐C−H bond of more challenging α‐silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.