Hydroaminoalkylation describes the atom-economical catalytic synthesis of amines by forming new Csp3 –Csp3 bonds using readily available amine and alkene feedstocks. Herein, we describe an earth-abundant and cost-efficient titanium catalyst generated in situ using commercially available Ti­(NMe2)4 and a simple to synthesize urea proligand. This system demonstrates high TOFs for hydroaminoalkylation with unactivated substrates and features easy to use commercially available titanium amido precursors. Additionally, a high catalytic activity, scope of reactivity, and regioselectivity are all demonstrated in the transformation of unactivated terminal olefins with various alkyl and aryl secondary amines. Finally, syntheses of useful amine-containing monomers suitable for the generation of amine-containing materials, as well as amine-containing building blocks for medicinal chemistry, are disclosed. These preparative methods avoid the necessity of glovebox techniques and are modified to be useful to all synthetic chemists.

Carboxylate esters have many desirable features as electrophiles for catalytic cross‐coupling: they are easy to access, robust during multistep synthesis, and mass‐efficient in coupling reactions. Alkenyl carboxylates, a class of readily prepared non‐aromatic electrophiles, remain difficult to functionalize through cross‐coupling. We demonstrate that Pd catalysis is effective for coupling electron‐deficient alkenyl carboxylates with arylboronic acids in the absence of base or oxidants. Furthermore, these reactions can proceed by two distinct mechanisms for C−O bond activation. A Pd0/II catalytic cycle is viable when using a Pd0 precatalyst, with turnover‐limiting C−O oxidative addition; however, an alternative pathway that involves alkene carbopalladation and β‐carboxyl elimination is proposed for PdII precatalysts. This work provides a clear path toward engaging myriad oxygen‐based electrophiles in Pd‐catalyzed cross‐coupling.

A dimer with two PdII–Me fragments is stabilized by the bridging coordination of the supporting 1-azaallyl/phosphine ligand. Heating the complex results in C­(sp3)–C­(sp3) bond formation and the release of ethane. Two different palladium products are generated, each with distinct coordination modes of the 1-azaallyl/phosphine ligand.

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Titanium-catalyzed hydroaminoalkylation has emerged as an atom-economical, earth-abundant synthesis of N-containing products.