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Synthesis of 1,2-Oxazinanes via Hydrogen Bond Mediated [3 + 3] Cycloaddition Reactions of Oxyallyl Cations with
Lingbowei Hu1, Michael Rombola1, Viresh H Rawal1
1Department of Chemistry , University of Chicago , 5735 South Ellis Avenue , Chicago , Illinois 60637 , United States.
Abstract:
Reported herein is the development of [3 + 3] cycloaddition reactions between oxyallyl cations and nitrones to yield 1,2-oxazinane heterocycles. Oxyallyl cation intermediates, generated in situ from α-tosyloxy ketones in the presence of hexafluoro-2-propanol (HFIP), a cosolvent, and a base, are found to react with a range of nitrones to afford 1,2-oxazinanes in good to high yields. The reactions are catalyzed by hydrogen-bond donors such as phenols and squaramides, and dramatically higher diastereoselectivities are observed with 4-nitrophenol.
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