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The one‐pot synthesis of λ4‐dibenzothiophen‐5‐imino‐N‐dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh2(esp)2 (esp=α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid) generating a Rh‐coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good yields. We assumed that after formation of the corresponding N‐sulfonio aziridine, a ring expansion occurs via selective C−C bond cleavage and concomitant elimination of dibenzothiophene. Unexpectedly, a similar protocol transforms 1‐arylcyclobutenes into 1‐cyano‐1‐arylcyclopropanes. Our calculations indicate that aziridination is not favored in this case; instead, sulfilimine‐substituted cyclobutyl carbocations are initially formed, and these evolve to the isolated cyclopropanes via ring contraction. Both procedures are operationally simple, tolerate a range of functional groups, including oxidation‐sensitive alcohols and aldehydes, and enable the convenient preparation of valuable 15N‐labelled products. These results demonstrate the potential of 1 to provide alternative pathways for the selective transfer of N‐atoms in organic molecules. [ABSTRACT FROM AUTHOR]

The reactivity of 5‐(alkynyl)dibenzothiophenium salts 1 is explored in the presence of different nucleophiles, dienes, and under photochemical conditions. Reaction with lithium acetylides affords diynes in moderate yields; while depending on the substitution pattern, the reaction with sulfinates delivers either the alkyne transfer products, alkynyl sulfones, or β‐(sulfonium) vinyl sulfones through addition to the C−C triple bond. Similar behavior is observed when tosylamines are used as nucleophiles. Salts of general formula 1 also react with dienes to render the corresponding Diels‐Alder cycloadducts. The vinyl sulfonium salts obtained by these routes further react with nucleophiles through a Michael addition, dibenzothiophene elimination sequence. Alternatively, they also engage in photoinduced radical cyclizations to produce substituted phenanthrenes. Attempts to use this specific addition/radical cyclization sequence for the construction of the 6a,7‐dehydroaporphine skeleton present in several families of alkaloids are also described. [ABSTRACT FROM AUTHOR]