Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 48, Pages 15753-15759Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201403475
Keywords
oxygen; electron transfer; radical reactions; reaction mechanisms; synthetic methods
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Funding
- Ministry of Education, Culture, Sports, Science and Technology, Japan
- Grants-in-Aid for Scientific Research [25620074, 14J03546] Funding Source: KAKEN
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A Nef reaction has been developed that is conducted under mildly basic conditions with molecular oxygen as an oxidant, without the need for metal additives. Whereas nitroalkanes are converted into ketones in good yield, nitroalkenes are transformed into alpha, beta-unsaturated ketones in one-pot by double-bond isomerization followed by the oxygen-mediated Nef reaction. The reaction protocol is both mild and general, and tolerates acid-and base-labile functionality or protecting groups. When oxygen-saturated sol-vents are employed, the reaction completes within 20 min. Mechanistically, the addition of nitronate ion and molecular oxygen is proposed to proceed initially through a singleelectron transfer event, as indicated by radical clock experiments. This ultimately generates a putative 1,1-dioxirane, which reacts further with another nitronate ion to generate the ketone. Involvement of a 1,1-dioxirane is supported by intramolecular trapping experiments with sulfide at the gposition of the nitro-moiety.
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