Sandvoß Alexander, Wahl Johannes M
Department Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, 55128 Mainz, Germany.
Org Lett. 2023 Aug 11;25(31):5795-5799. doi: 10.1021/acs.orglett.3c02048. Epub 2023 Jul 28.
A variety of cyclic alcohols are found to undergo nitrogen insertion by subjection to -mesitylsulfonylhydroxylamine. Critical to a successful process is the use of fluorinated alcoholic solvents, which ensures sufficient substrate activation to allow engagement with the ambiphilic aminating agent. This transition-metal-free nitrogen insertion provides access to a variety of medicinally relevant heterocycles such as pyrrolidenes, quinolines, and benzazepines (24 examples). Furthermore, combination with a photochemical Norrish-Yang-type cyclization allows an unprecedented access to indoles from -substituted acetophenones.
发现多种环醇在受到间甲苯磺酰羟胺作用时会发生氮插入反应。成功进行该反应的关键是使用氟化醇类溶剂，这可确保底物得到充分活化，从而能够与双亲性胺化剂发生反应。这种无过渡金属的氮插入反应可用于合成多种与药物相关的杂环化合物，如吡咯烷、喹啉和苯并氮杂卓（24个实例）。此外，与光化学诺里什-杨型环化反应相结合，可实现从未经取代的苯乙酮出发，以前所未有的方式合成吲哚。
