Abstract

Metal- and base-free thiolation of the unactivated methyl C(sp3)–H bond in 2-picoline N-oxides with thiols is achieved by a one-pot, two-step sequence, including a TFAA-mediated [3,3]-sigmatropic rearrangement of pyridine N-oxides and TBAB-catalyzed direct conversion of trifluoroacetates into thioethers.

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