Light‐Induced Ruthenium‐Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N‐Acyl Sulfimides and Sulfoximines

Abstract

1,4,2-Dioxazol-5-ones are five-membered heterocycles known to decarboxylate under thermal or photochemical conditions, thus yielding N-acyl nitrenes. Described herein is a light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2-dioxazol-5-ones at room temperature, thus providing direct access to N-acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one-pot sulfur imidation/oxidation sequence catalyzed by a single ruthenium complex is reported.

Synthesis of Sulfoximine Carbamates by Rhodium-Catalyzed Nitrene Transfer of Carbamates to Sulfoxides

“…Therefore, Bolm developed the use of 1,4,2-dioxazol-5-ones to transfer a range of amides requiring photochemical activation and a Ru catalyst (Scheme 1c). 18 Richards reported a Rh-catalyzed method for the direct preparation of NH-sulfoximines using O-(2,4-dinitrophenyl)-hydroxyl-amine with Rh 2 (esp) 2 as the catalyst. 19 Methods for N-functionalization of NH-sulfoximines have also undergone significant recent development, including methods for Narylation, 20 acylation, 21 alkynylation, 22 and alkylation.…”

Cp*CoIII‐Catalyzed C(sp3)−H Bond Amidation of 8‐Methylquinoline

“…Our exploration on the use of first row transition metals for CÀHb ond functionalization [16] prompted us to investigate direct amidation of C(sp 3 )ÀHb onds using Cp*Co III based catalysts. Here we report the first efficient, mild, and oxidantf ree Cp*Co-catalyzed C(sp 3 )ÀHb ond amidation of 8-methylquinoline using aryl/alkyl oxazolones [17] as an amidatinga gent (Scheme1).…”

Cationic Cobalt(III)‐Catalyzed Aryl and Alkenyl CH Amidation: A Mild Protocol for the Modification of Purine Derivatives

“…After as eries of preliminarys creening, we were pleased to findt hat the desired amidation product (3a)c ould be obtained in 70 %y ield using 3-phenyl-1,4,2-dioxazol-5-one [(SbF 6 ) 2 ]-the preparation and catalysis of which were firstly reported by Glorius [8a] -as the catalyst (5 mol %) in DCE under air (Table 1, entries 1-6). [16] The direct CÀN bond formation by using 1,4,2-dioxazol-5-one reagents has been elegantly developed by the groups of Bolm, [17] DubØ, [18] and Chang. [15] Similar to acyl azides, they are knownt og enerate N-acyl nitrenes throught hermalo rp hoto-initiated decomposition, which makes them av ery good nitrenes ources.…”