Nickel-Catalyzed Denitrogenative Cyclization of 1,2,3,4-Benzothiatriazin-1,1(2H)-dioxides with Arynes To Synthesize Biaryl Sultams

Abstract

Herein, we report the nickel-catalyzed denitrogenative cyclization reaction of 1,2,3,4-benzothiatriazine-1,1-dioxides with arynes to generate the polysubstituted biaryl sultams with tolerance of a wide diversity of substituents on every subunit. The mechanistic study indicates that the reaction is initiated by the formation of a diradical species, which reacts with a nickel complex to form a nickelacycle intermediate and carries out the subsequent cyclization through insertion of an aryne.

Design of Stereogenic‐at‐Iron Catalysts with a (3+2+1)‐Ligand Sphere

“…Optical rotations were measured with a Krüss P8000-T polarimeter with [α] D 22 values listed in degrees with concentrations reported in g/100 mL. 6-Bromo-2,2'-bipyridine [20] and N-mesityl-2-nitrobenzenesulfonamide [21] were synthesized according to reported procedures.…”

Rhodium-Catalyzed Annulations and Heck Coupling/Aza-Michael Addition for the Synthesis of Benzothiadiazinoisoquinoline 6,6-Dioxides and Benzothiadiazinoisoindole 5,5-Dioxides, Respectively

“…Over the decades, metal-catalyzed C–H annulation reactions are used as energetic tools to construct a fused polyheteroaromatic ring in organic synthesis . In this context, the synthesis of various nitrogen-based five/six-membered heterocycles including indoles, isoquinolines, pyridines, isoquinolones, and quinazolinones has been developed. − Apart from the heterocycles, the utilization of benzothiadiazine dioxides/dihydrobenzothiadiazine dioxides is rare and remains to be developed in metal-catalyzed organic synthesis.…”

One-Pot Synthesis of Polycyclic Sultams Enabled by Gold-Catalyzed Hydroamination of o-Alkynylbenzenesulfonamides and Subsequent Iodine(III)-Mediated Counteranion-Assisted Intramolecular Annulation

“…To the best of our knowledge, only one example has been reported by Hsieh's group in 2022, involving nickel-catalyzed denitrogenative cyclization reaction of 1,2,3,4benzothiatriazine-1,1-dioxides with arynes to deliver the polysubstituted biaryl sultams (Scheme 1a). 14 This method requires a nitrogen atmosphere to maintain the reactivity of the nickel catalyst as well as high temperature (up to 80 °C) and long reaction times. In fact, high temperature and long reaction times are generally required for most transition-metal-catalyzed syntheses of sultams.…”

“…As a result, these heterocyclic structures play a crucial role in medicinal, organic synthetic, and agricultural fields and have attracted great attention from synthetic chemists for a long time. Consequently, various methodologies, particularly those employing transition metals such as Pd, Rh, Co, Ag, Au, Ni have been developed to access these sultam skeletons. These facile and effective methods usually provide the desired sultams through fewer synthetic steps.…”

“…While a variety of functional sultams can be prepared using different pathways, there are limited methodologies for synthesizing polycyclic sultams containing multiple polycyclic aromatic structures. To the best of our knowledge, only one example has been reported by Hsieh’s group in 2022, involving nickel-catalyzed denitrogenative cyclization reaction of 1,2,3,4-benzothiatriazine-1,1-dioxides with arynes to deliver the polysubstituted biaryl sultams (Scheme a) . This method requires a nitrogen atmosphere to maintain the reactivity of the nickel catalyst as well as high temperature (up to 80 °C) and long reaction times.…”