A cascade indazolone-directed Ir(iii)- and Rh(iii)-catalyzed C(sp²)–H functionalization/[4 + 2] annulation of 1-arylindazolones with sulfoxonium ylides to access chemically divergent 8H-indazolo [1,2-a]cinnolines

Abstract

The indazolones directed chemoselective synthesis of 8H-indazolo [1,2-a]cinnolines have been realized via cascade Cp*Ir(III)- and Cp*Rh(III)-catalyzed C-H activation/cyclization reaction of 1-arylindazolones with sulfoxonium ylides. The strategy showcased broad substrate scope,...

Cp*Rh(III)-Catalyzed ortho-Alkylation/Alkenylation of Nitroarenes

“…10 The reported reactions mainly include the Rh(III)-catalyzed orthoalkynylation of nitroarenes (Scheme 2b-1), cascading Rh(III)catalyzed C−H activation, alkyne insertion, and rearrangements to synthetic oxindole (Scheme 2b-2). Driven by our continuous interest in Rh(III)-catalyzed C−H activation, 11 herein, we report the first example of the Cp*Rh(III)-catalyzed C−H bond alkylation/alkenylation reaction of nitroarene with maleimide and methyl acrylate (Scheme 2c). These reactions employ commercially available starting materials and reagents and tolerate a wide range of functional groups.…”

A Platform for the Synthesis of Diverse Phosphonyl and Thiofunctionalized Sulfoxonium Ylides

“…If successful, this would offer an alternative approach for the synthesis of functionalized sulfoxonium ylides, particularly for the phosphonylation, trifluoromethylthiolation, and dithiocarbanation of sulfoxonium ylides. As a continuation of our interest in sulfoxonium ylides, herein we report a practical strategy for the construction of diverse phosphonyl and thiofunctionalized sulfoxonium ylides via controllable monofunctionalization of hybrid I (III) /S (VI) ylides (Scheme d). Compared to our previous work, the reaction primarily relies on nucleophilic substitution of the substrate by the negatively charged sulfur or phosphorus ion under kinetic control.…”

Divergent Synthesis of Tetrasubstituted Phenols via [3 + 3] Cycloaddition Reaction of Vinyl Sulfoxonnium Ylides with Cyclopropenones

“…In 2022, Vaitla and co-workers achieved the multisubstituted phenols synthesis via a Ru-catalyzed [4 + 2] benzannulation of vinyl sulfoxonium ylide with electron-deficient alkynes and alkenes, in which vinyl sulfoxonium ylide served as a C4-synthon and underwent a Diels–Alder reaction to construct the six-membered benzene ring (Scheme b). Considering the vital role of multisubstituted phenols in pharmaceutics and driven by our continuous interest on the versatile transformations of sulfoxonium ylides, herein we developed the first example of a switchable [3 + 3] cycloaddition reaction between vinyl sulfoxonium ylides and cyclopropenones to produce tetrasubstituted phenols (Scheme c). In this work, 2,3,4,5-tetrasubstituted phenols (total 14 examples) were obtained when the reaction was catalyzed by copper salts in dioxane, while 2,3,5,6-tetrasubstituted phenols (total 18 examples) were produced under metal-free conditions.…”