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.

Comparative Catalytic Activity of Group 9 [Cp*MIII] Complexes: Cobalt‐Catalyzed CH Amidation of Arenes with Dioxazolones as Amidating Reagents

“…[7b, 10] Recently,w er eported ar hodium(III)-catalyzed CÀH amidation protocol with dioxazolones as robust and highly efficient amidating reagents. [11] Dioxazolones, [12] while safe Scheme 1. Direct CÀHbond functionalization with [Cp*M III ]systems.…”

Rhodium(III)‐Catalyzed Amidation of Unactivated C(sp3)H Bonds

“…We now report am ild rhodium(III)-catalyzed C(sp 3 ) À Ha midation for ab road scope of substrates,i ncluding 8-alkylquinoline and aliphatic cyclic and acyclicketoximes.This amidation reaction utilizes 3-substituted 1,4,2-dioxazol-5-ones [15] as the amide sources,a nd they are particularly attractive nitrenetransfer reagents owing to their high activity,s tability,a nd synthetic accessibility (Scheme 1b). [16] We initiated our studies with the screening of reaction conditions in the coupling of 8-methylquinoline (1a)w ith 3phenyl-1,4,2-dioxazol-5-one (2a;T able 1). Using [{RhCp*Cl 2 } 2 ]/AgSbF 6 as ac atalyst, coupling occurred in DCE (entry 1) to afford the product 3aa in 76 %y ield.…”

Comparative Catalytic Activity of Group 9 [Cp*MIII] Complexes: Cobalt‐Catalyzed CH Amidation of Arenes with Dioxazolones as Amidating Reagents

“…[1] This approach does not require prefunctionalized starting materials that have to be prepared in separate steps.Consequently,adiverse range of transition-metal catalytic systems has been developed for such transformations,including Pd, [2] Rh, [3] Ru, [4] and Ir catalysts. [11] Dioxazolones, [12] while safe Scheme 1. [6] Since pioneering studies by Kanai and co-workers on the use of a[ Cp*Co III ]c atalyst for CÀHa ctivation, [7] ah andful of cobalt(III)-catalyzed reactions for direct functionalization have been developed with high synthetic potential.…”

“…[6] Since pioneering studies by Kanai and co-workers on the use of a[ Cp*Co III ]c atalyst for CÀHa ctivation, [7] ah andful of cobalt(III)-catalyzed reactions for direct functionalization have been developed with high synthetic potential. [11] Dioxazolones, [12] while safe Scheme 1. [8b,f] Ford irect C À Ha midation, which has been the focus of extensive recent research, the [Cp*Co III ]s ystem is effective only with 2-phenylpyridine and its pyrimidylindole derivatives.…”