Mechanochemical Conditions for Intramolecular N−O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides

Angewandte Chemie International Edition, vol. 63, pp. e202413181

Abstract

Starting from N-acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N-O couplings to provide unprecedented 1,3,2,4-oxathiadiazole 3-oxides in good to excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % in the presence of phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required in this solvent-free procedure. Under heat or blue light, the newly formed five-membered heterocycles function as nitrene precursors reacting with sulfoxides as exemplified by the imidation of dimethyl sulfoxide.

Authors 6

1. Shulei Pan Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

2. Peng Wu Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

3. Dimitra Bampi Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

4. Jas S. Ward

   University of Jyväskylä

   Affiliation as printed

   University of Jyvaskyla Department of Chemistry P.O. Box. 35, Survontie 9 B 40014 Jyväskylä Finland

5. Kari T. Rissanen

   University of Jyväskylä

   Affiliation as printed

   University of Jyvaskyla Department of Chemistry P.O. Box. 35, Survontie 9 B 40014 Jyväskylä Finland

6. Carsten Bolm corresponding Aachen Institute of Organic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Organic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   RWTH Aachen University: Rheinisch-Westfalische Technische Hochschule Aachen, Chemistry, Landoltweg 1, 52056 Aachen, GERMANY