PIFA‐Mediated C─H Thiolation and Selenylation of <i>Pseudo</i> ‐Anomeric Position of Glycals with Disulfides or Diselenides at Room Temperature

Abstract Herein, we report the [Bis(trifluoroacetoxy)iodo]benzene mediated C(sp 2 )−H bond thiolation and selenylation of pseudo ‐anomeric position of C2‐branched glycals using sugar, aliphatic, and aromatic disulfides or diselenides partner at room temperature. This developed protocol offers a metal‐free synthetic route that potentiates the generation of a library of 1‐thiotrehaloses and thio/selenoglycosides bearing a variety of functional groups in moderate to good yields. Concerning the glycal partners, the peracetylated protected analogue showed a similar reactivity like the benzylated model substrates under this conditions. Based on control experiments, a plausible radical pathway mechanism is proposed.