The Regioselective and Diastereoselective Direct Addition of Amines to Alkenes Using a Tantalum-Ureate Hydroaminoalkylation Catalyst

An
organometallic tantalum catalyst equipped with a ureate
ligand
achieves the atom-economic hydroaminoalkylation (HAA) reaction to
regioselectively form Csp3–Csp3 bonds
by adding C–H activated unprotected secondary amines across
alkenes. The substrate scope of this catalyst includes a range of
activated, unactivated, and conjugated terminal, geminal and internal
alkenes with aromatic, aliphatic and N-heterocyclic amines. This broad
diversity of compatible substrates illustrates that hydroaminoalkylation
offers a useful solution to the longstanding challenge of identifying
a general catalyst for directly and catalytically adding amines to
alkenes. This catalyst mediates hydroaminoalkylation with controlled
regioselectivity and also achieves the challenging dialkylation of
select amines with superb diastereoselectivity, including the selective trans-dialkylation of N-heterocycles.