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Stereodefined oxygen‐substituted 1,2‐oxazines were prepared by three different routes. The cycloaddition of enol ethers such as 1 with α‐nitrosoalkenes generated in situ gave the heterocycles 3 and 4. Acid‐catalysed additions of alcohols to the 6H‐1,2‐oxazines 5 led to mixtures of the adducts 6 and the substitution products 7 with moderate chemoselectivity. Epoxidation of the 6H‐1,2‐oxazines 5 proceeded...
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