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The mechanistic pathway for the formation of 1,2-oxazetes by reaction of olefins with nitrous anhydride has been clarified. The initial reaction intermediate, a β-nitroso nitrite ester that is sensitive to light, undergoes O-NO fission to form a β-nitroso alkoxy radical, even with ambient fluorescent lighting but much faster with blue light irradiation. The oxygen of the alkoxy radical subsequently adds to the adjacent nitroso group to generate a cyclic four-membered nitrosyl radical. The 1,2-oxazete is then produced by elimination to generate the C═N bond. No 1,2-oxazete formation occurs in the dark.
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| http://dx.doi.org/10.1021/acs.orglett.2c04080 | DOI Listing |
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