A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C—H oxidation reaction for the synthesis of <i>anti-</i>oxazolidinones from simple <i>N</i>-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg. 63%) and excellent diastereoselectivities (avg. 15:1) to furnish products with different regiochemistry from those previously obtained using allylic C—H amination reactions. We present applications of this method to the synthesis of hydroxyamino acids, individually and as a late-state strategy for the formation of amino alcohol motifs in peptide settings, as well as the synthesis of a biologically relevant amino sugar. This process marks the first use of an aprotic, non-acidic nucleophile in a Pd(II) / sulfoxide catalyzed allylic C-H oxidation. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C—H cleavage and π-allylPd functionalization with a weak oxygen nucleophile, and to promote catalyst regeneration.

N Boc amines to oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted acid co-catalyzed allylic C−H oxidation

249th National Meeting (2015)

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