Recently, our group discovered that simple [Ti=NR] (imido) complexes are capable of alkyne carboamination via the oxidative 3-component coupling of alkynes, nitrenes (from PhNNPh), and alkenes, ultimately delivering hard-to-access α,β-unsaturated imines. Detailed mechanistic studies will be presented that shed light on the unique mechanism of this reaction, which proceeds through [2+2] Ti=NR + alkyne cycloaddition followed by alkene insertion to form a key semi-saturated diazatitanacyclohexene intermediate. Ongoing studies into the collapse of this intermediate into the α,β-unsaturated imine product will also be discussed, including the crystallographic characterization and stoichiometric reactivity of model titanocene diazatitanacyclohexene complexes. Finally, this work will be compared to related redox-neutral carboamination reactions that are catalyzed by Ti and Zr, along with a forward outlook on expanding both reactions.

Ti-catalyzed alkyne carboamination: Revisiting strategies to make α,β-unsaturated imines

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.