Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Divergent Rhodium-Catalyzed Cyclization Reactions of Enoldiazoacetamides with Nitrosoarenes

Divergent Rhodium-Catalyzed Cyclization Reactions of Enoldiazoacetamides with Nitrosoarenes
Michael P. Doyle, Hadi Arman, Daniel Wherritt, Marianne Lankelma, Qing-Qing Cheng
The first cyclization reactions of enoldiazo compounds with nitrosoarenes have been developed. Under the catalysis of rhodium(II) octanoate, [3 + 2]-cyclization between enoldiazoacetamides and nitrosoarenes occurred through cleavages of the enol double bond and the amide bond, thus furnishing fully substituted 5-isoxazolone derivatives. Upon changing the catalyst to rhodium(II) caprolactamate, the reaction pathway switched to an unprecedented formal [5 + 1]-cyclization that provided multifunctionalized 1,3-oxazin-4-ones with near exclusivity under otherwise identical conditions. Mechanistic studies uncovered distinct catalytic activities and reaction intermediates, which plausibly rationalized the novel reactivity and catalyst-controlled chemodivergence. Furthermore, a mechanism-inspired enantioselective rhodium-catalyzed reaction of γ-substituted enoldiazoacetamide with nitrosobenzene produced highly enantioenriched heterocycle-linked trialkylamine.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05840

DOI: 10.1021/jacs.7b05840

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