Sulfoximine Directed Intermolecular o-C–H Amidation of Arenes with Sulfonyl Azides

Abstract

The Ru(II)-catalyzed intermolecular o-C-H amidation of arenes in N-benzoylated sulfoximine with sulfonyl azides is demonstrated. The reaction proceeds with broad substrate scope and tolerates various functional groups. Base hydrolysis of the amidation product provides the anthranilic acid derivatives and methylphenyl sulfoximine (MPS) directing group. This method is successfully employed for the synthesis of HMR 1766.

Ruthenium‐Catalyzed Direct CH Amidation of Arenes Including Weakly Coordinating Aromatic Ketones

“…Despite these achievements, however, the ruthenium‐catalyzed CH bond activation strategy has been practiced almost exclusively for the introduction of alkyl, vinyl, or aryl groups 6b. 8d In fact, intermolecular direct CH amination of arenes mediated by ruthenium species still remains largely unexplored 10. 11…”

“…[6b, 8d] In fact, intermolecular direct CÀH amination of arenes mediated by ruthenium species still remains largely unexplored. [10,11] Along with our continuous efforts on the development of highly efficient direct amination reactions, [12] we recently reported a new approach of rhodium-catalyzed direct sp 2 CÀH amination by using azides as the amino source, thus releasing molecular nitrogen as a single byproduct. [13] The developed procedure was successfully applied to the amination of various arene substrates without requiring external oxidants.…”

Ruthenium‐Catalyzed Hydroarylation and One‐Pot Twofold Unsymmetrical C−H Functionalization of Arenes

“…[11][12][13] However,the use of air-stable and low-cost ruthenium catalysts for intramolecular hydroarylation with unactivated alkenes remains underdeveloped. Herein, we discuss the methyl phenyl sulfoximine (MPS; 1)directed [15,16] ruthenium-catalyzed intramolecular hydroarylation of an Otethered olefin bearing benzoic acid derivatives for the synthesis of aw ide array of dihydrobenzofurans at room temperature (Scheme 2b). Ther eaction involves an intramolecular ortho-CÀHhydroarylation and intermolecular functionalization of as econd ortho-CÀHb ond.…”

Directing‐Group‐Assisted Transition‐Metal‐Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

“…The N ‐acyl group was employed to accomplish the C−H amidation process. Sahoo and co‐workers demonstrated Ru‐catalyzed sulfoximine directed intermolecular C−H amidation of N ‐benzoylated sulfoximine with sulfonyl azides or N ‐OTs phthalimide ,. Stoichiometric KOAc or Ag 2 O as base additives were required to enhance to the efficiency.…”