The unexpected 4,1-hydroaminoalkylation of dienes provides selective access to linear homoallylic amines by zirconium catalysis. This switch from the traditional branched preferred regioselectivity to selective linear product formation using this early transition metal can be attributed to π-allyl intermedia

Catalyst and substrate steric and electronic features that influence regioselectivity in hydroaminoalkylation were leveraged to develop a synthetic approach for the selective synthesis of β-amino acids. An in situ generated tantalum-ureate catalyst was used to prepare 18 γ-silylated amines in up to 93% yield from internal silylated alkenes. β-Amino silane regioisomer production was rarely observed, making this work one of the few examples of highly regioselective hydroaminoalkylation with unsymmetric internal alkenes. These γ-amino silanes were converted to γ-amino alcohols with a modified Tamao–Fleming oxidation strategy followed by two additional steps to prepare β-amino acids, including a key fragment of the anticancer drug candidate Ipatasertib.