Sulfoximine Aided Ru(II)-Catalyzed Asymmetric Double C(sp)-H Hydroarylations of Olefins.

Presented here is a sulfoximine-directed Ru(II)-catalyzed asymmetric intramolecular double C(sp)-H hydroarylation of olefins. This process provides a diastereoselective and enantiospecific synthetic route to highly substituted tetrahydrobenzodifurans. Notably, the reaction accommodates labile functional groups and is scalable to gram quantities.

A Three-Component Arene Difunctionalization: Merger of C(sp )/(sp )-H Bond Addition.

A tandem three-component C-H bond addition involving the activation of an inert C(sp )-H bond is reported. The process enables the direct regioselective synthesis of 1,2-difunctionalized arenes with the formation of C(sp )- and C(sp )-C(arene) bonds. 2-Iodobenzoic acid derivatives behave as masked bifunctional reagent (BFR) and react with 2-pyridyl-methyl sulfoximine (MPyS) protected aliphatic acids bearing α,α-disubstituted groups, and alkenes to produce β-aryl-δ-alkenyl amide derivatives in a single operation.

Probing Chiral Sulfoximine Auxiliaries in Ru(II)-Catalyzed One-Pot Asymmetric C-H Hydroarylation and Annulations with Alkynes.

Developed herein is a chiral sulfoximine-enabled Ru(II)-catalyzed asymmetric C-H activation/functionalization involving intramolecular hydroarylation and functionalization/annulation of alkynes. This process constructs dihydrobenzofuran- or indoline-fused isoquinolinones having a tertiary or quaternary stereocenter with good yields and enantioselectivities (up to 97:3 enantiomeric ratio). The chiral sulfoxide precursor used in synthesizing the enantiopure sulfoximines is spontaneously eliminated during the reaction.

Sulfoximine Assisted C-H Activation and Annulation via Vinylene Transfer: Access to Unsubstituted Benzothiazines.

In this study, we report the synthesis of unsubstituted 1,2-benzothiazines through a redox-neutral Rh(III)-catalyzed C-H activation and [4+2]-annulation of S-aryl sulfoximines with vinylene carbonate. Notably, the introduction of an N-protected amino acid ligand significantly enhances the reaction rate. The key aspect of this redox-neutral process is the utilization of vinylene carbonate as an oxidizing acetylene surrogate and an efficient vinylene transfer agent.