indoles

synthesized

enantioselective

crack_117679

rh iii catalyzed

diastereoselective

polymer nanocomposites

organocatalytic

rhodium iii

swine

dearomatization

azides

ring opening

rhodium catalyzed

preimplantation

modernity

mechanochemical

Journal of the American Chemical Society

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.

Divergent Rhodium-Catalyzed Cyclization Reactions of Enoldiazoacetamides with Nitrosoarenes