21555-07-7Relevant academic research and scientific papers
α-Oxo-Ketenimines from Isocyanides and α-Haloketones: Synthesis and Divergent Reactivity
Mamboury, Mathias,Wang, Qian,Zhu, Jieping
supporting information, p. 12744 - 12748 (2017/09/25)
The palladium-catalyzed reaction of α-haloketones with isocyanides afforded α-oxo-ketenimines through β-hydride elimination of the β-oxo-imidoyl palladium intermediates. Reaction of these relatively stable α-oxo-ketenimines with nucleophiles such as hydrazines, hydrazoic acid, amines, and Grignard reagent afforded pyrazoles, tetrazole, β-keto amidines, and enaminone, respectively, with high chemoselectivity. Whereas amines attack exclusively on the ketenimine functions, the formal [3+2] cycloaddition between N-monosubstituted hydrazines and α-oxo-ketenimines was initiated by nucleophilic addition to the carbonyl group.
