An Orchestrated Unsymmetrical Annulation Episode of C(sp²)–H Bonds with Alkynes and Quinones: Access to Spiro-isoquinolones

A nontrivial Ru-catalyzed one-pot sequential oxidative coupling of a (hetero)­arene/vinylic/chromene system with alkyne and quinone is presented; the methyl phenyl sulfoximine (MPS) directing group is vital. This cyclization forms four (two C–C and two C–N) bonds in a single operation and produces unusual spiro-fused-isoquinolones with a broad scope. The release of phenyl methyl sulfoxide makes the MPS group transformable. A deuterium scrambling study sheds light on the reaction path

Transformable Sulfoximine Assisted One-Pot Double Annulation of Vinylic C–H Bonds with Unactivated Alkynes

The methylphenyl sulfoximine (MPS) directing group (DG) successfully promotes the one-pot double annulation of acrylic acids with alkynes under Ru catalysis, which is unprecedented. Diverse arrays of pyrido-fused-isoquinolinone skeletons are fabricated from acrylamides, creating two C–C and two C–N bonds in a single operation. The unsymmetrical annulation with two distinct alkynes is presented. The recovery of methylphenyl sulfoxide, a precursor of MPS, validates the synthetic adaptability of transformable-DG (T^fDG) in C–H activation

Transformable Sulfoximine Assisted One-Pot Double Annulation of Vinylic C–H Bonds with Unactivated Alkynes

The methylphenyl sulfoximine (MPS) directing group (DG) successfully promotes the one-pot double annulation of acrylic acids with alkynes under Ru catalysis, which is unprecedented. Diverse arrays of pyrido-fused-isoquinolinone skeletons are fabricated from acrylamides, creating two C–C and two C–N bonds in a single operation. The unsymmetrical annulation with two distinct alkynes is presented. The recovery of methylphenyl sulfoxide, a precursor of MPS, validates the synthetic adaptability of transformable-DG (T^fDG) in C–H activation

Sulfoximine-Directed Ruthenium-Catalyzed <i>ortho</i>-C–H Alkenylation of (Hetero)Arenes: Synthesis of EP3 Receptor Antagonist Analogue

The reusable sulfox­imine directing-group-assisted Ru­(II)-catalyzed chemo- and regio­selective <i>ortho</i>-C–H alkenylation of arenes and hetero­arenes with acrylates and α,β-unsaturated ketones/vinyl sulfone is shown. The <i>N</i>-aroyl sulfoximine undergoes annulation with diphenyl­acetylene, delivering iso­quinoli­nones and methyl phenyl sulfoxide. The present protocol is successfully employed for the synthesis of the EP3 receptor antagonist analogue

Ru-Catalyzed One-Pot Diannulation of Heteroaryls: Direct Access to π‑Conjugated Polycyclic Amides

A novel Ru-catalyzed oxidative double annulation of heteroarenes with symmetrical and unsymmetrical alkynes is reported. A general method for the unsymmetrical annulation of heteroarenes with two distinct alkynes is showcased for the first time. Methylphenyl sulfoximine (MPS) plays an important role in the annulations of heteroarenes and allows the construction of structurally complex π-conjugated heteroarene-fused polycyclic amide skeletons via the formation of multiple C–C and C–N bonds in a single operation. The reaction exhibits excellent substrate scope and tolerates a wide range of functional groups

Ruthenium-Catalyzed <i>ortho</i>-C–H Mono- and Di-imidation of Arenes with <i>N</i>‑Tosyloxyphthalimide

The Ru­(II)-catalyzed imidation of the <i>o</i>-C–H bond in arenes with <i>N</i>-tosyloxyphthalimide is realized with the assistance of a methyl phenylsulfoximine (MPS) directing group. This method is applicable to access the hitherto difficult <i>o</i>-C–H di-imidation products. The sequential C–N and C–C bond formation of <i>o</i>-C–H arenes creates peripherally decorated benzoic acid derivatives. The readily removable MPS-DG and easily modifiable phthaloyl moiety make this strategy synthetically viable for constructing highly functionalized C–N bearing arenes and heteroarenes