Nitrenium ions: structure and reactivity

Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

“…However, using umpolung reactivity of sulfur, we have shown here that direct CÀS coupling was possible via generation of sulfenium ion [12b] and subsequent utilization of them for aromatic electrophilic substitution (EArS) reactions ( Figure 2b). The sulfenium ion can be considered as the sulfur analogue of carbenium [30] or nitrenium ions [30][31] and are generally prepared by activation of S-arylthiophthalimides. [12,32] However, we have shown here that no prefunctionalization of the substrates or any template approach were necessary for this cross dehydrogenative CÀS coupling reaction of arenes and thiols, and the sulfenium ions could be generated in situ by oxidation of thiols.…”

Steric and Electronic Effect on C2‐H Arylation of Sulfonamides

“…The nitrenium ions are isoelectronic with carbenium ions and their use in organic synthesis have expanded recently . The nitrenium ions can be generated using iodine(III) oxidant via ligand exchange at the iodine center to form an intermediate i. e., amido‐λ 3 ‐iodane .…”

Soft–Hard Acid–Base‐Controlled C−H Trifluoroethoxylation and Trideuteriomethoxylation of Anilides

“…However, in this work the solvents 2,2,2‐trifluoroethanol (TFE) and [D 4 ]MeOH (CD 3 OD) led to selective incorporation at para position of anilides by C−O bond formation. These reactions were favored due to hard–hard preference by the alcohols with harder carbenium ions over the softer nitrenium ions . Thus the role of SHAB principle is clearly established for the dehydrogenative C−O bond formation of anilides.…”