4208-45-1Relevant 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.
Unexpected Role of p-Toluenesulfonylmethyl Isocyanide as a Sulfonylating Agent in Reactions with α-Bromocarbonyl Compounds
Chen, Jiajia,Guo, Wei,Wang, Zhenrong,Hu, Lin,Chen, Fan,Xia, Yuanzhi
, p. 5504 - 5512 (2016/07/13)
The reactions of p-toluenesulfonylmethyl isocyanide (TosMIC) with α-bromocarbonyl compounds leading efficiently to α-sulfonated ketones, esters, and amides were reported, in which an explicit new role of TosMIC as the sulfonylating agent was uncovered for the first time. Mechanistic study by control experiments and DFT calculations suggested that the reaction is initiated by Cu(OTf)2-catalyzed hydration of TosMIC to form a formamide intermediate, which undergoes facile C-S bond cleavage under the mediation of a Cs2CO3 additive.
