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.

中文翻译：

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N-(磺基)硫亚胺试剂：用于骨架编辑的亲电氮原子的非氧化源

报道了多克规模的 λ4-二苯并噻吩-5-亚氨基-N-二苯并噻吩鎓三氟甲磺酸盐 (1) 的一锅法合成。该化合物与 Rh2(esp)2（esp = α,α,α′,α′-四甲基-1,3-苯二丙酸）反应生成 Rh 配位的磺氮烯物质，该物质能够将亲电氮烯部分转移到烯烃上。当使用茚作为底物时，可以以良好的收率获得异喹啉。我们假设在形成相应的 N-磺基氮丙啶后，通过选择性 C-C 键断裂并同时消除二苯并噻吩而发生扩环。出乎意料的是，类似的方案将 1-芳基环丁烯转化为 1-氰基-1-芳基环丙烷。我们的计算表明，在这种情况下，氮丙啶化不受欢迎；相反，最初形成硫亚胺取代的环丁基碳阳离子，并通过环收缩演变成分离的环丙烷。这两种方法操作简单，可耐受一系列官能团，包括氧化敏感的醇和醛，并且能够方便地制备有价值的 15N 标记产品。这些结果表明 1 有可能为有机分子中 N 原子的选择性转移提供替代途径。