Advances in transition metal-catalyzed C-H amination strategies using anthranils.

Modern times have witnessed an uprise in the synthesis and derivatization of nitrogen-containing fused heterocycles. Amination reactions involving nitrene chemistry have always been the most convenient choice for the incorporation of a nitrogen atom in a molecule. The utilization of an open nitrene species harnesses harsh conditions. Hence, transition metal-catalyzed C-H amination reactions using aminating agents have been an attractive choice. Electrophilic aminating agents for C-H amination reactions are well exploited due to their desirable reaction conditions. Out of all, anthranils have paved the way forward due to their utility in simultaneously forming two new functional groups (amine and carbonyl). Amination using anthranils follows a metal-nitrenoid pathway. Often, the amination has been followed by a Lewis acid or transition metal-mediated intramolecular cyclization to directly produce fused heterocycles. This review broadly demonstrates the utilization of anthranils as an aminating agent for transition metal-catalyzed C-H amination reactions. The focus has been given to the scope, limitations, and mechanistic understanding of using such an electrophilic aminating agent, anthranil, with transition metals.

Harnessing Vinyl Acetate as an Acetylene Equivalent in Redox-Neutral Cp*Co(III)-Catalyzed C-H Activation/Annulation for the Synthesis of Isoquinolones and Pyridones.

We have developed Cp*Co(III)-catalyzed redox-neutral synthesis of 3,4-unsubstituted isoquinoline 1(2H)-ones at ambient temperature using N-chloroamides as a starting material. The reaction utilizes vinyl acetate as an inexpensive and benign acetylene surrogate. The N-Cl bond of the N-chlorobenzamides plays the role of an internal oxidant and hence precludes the need for an external oxidant. The reaction works with a wide range of substrates having various functional groups and a substrate containing a heterocyclic ring. Notably, the reaction is extended to the N-chloroacrylamides in which vinylic C-H activation occurs to furnish the 2-pyridone derivatives. Preliminary mechanistic studies were also conducted to shed light on the mechanism of this reaction.

Free Amine-Directed Ru(II)-Catalyzed Redox-Neutral [4 + 2] C-H Activation/Annulation of Benzylamines with Sulfoxonium Ylides.

An external oxidant free Ru(II)-catalyzed C-H functionalization/annulation of primary benzylamines with sulfoxonium ylides has been developed for the synthesis of isoquinolines. The reaction utilizes free amine as a directing group, which is generally considered to be a poor directing group. This work presents the first example of Ru-catalyzed C-H functionalization of benzylamines under redox-neutral conditions. The detection of the amine-directed ruthenacyclic intermediate using high-resolution mass spectrometry corroborated the involvement of free amine as a directing group.

Cp*Co(III)-catalyzed C-H amination/annulation cascade of sulfoxonium ylides with anthranils for the synthesis of indoloindolones.

Cp*Co(iii)-catalyzed [4+1] annulation of sulfoxonium ylides with anthranils has been developed for the synthesis of indole-indolone scaffolds. The dual functionality of anthranils was exploited, wherein the nitrogen has been used for C-H amination and the aldehyde group was utilized in the subsequent intramolecular aldol condensation to furnish the corresponding annulated products.

Catalyst- and reagent-free 1,6-hydrophosphonylation of p-quinone methides: a practical approach for the synthesis of diarylmethyl phosphine oxides.

We developed a catalyst-, reagent-, and additive-free protocol with 100% atom economy for the synthesis of diarylmethyl phosphine oxides via 1,6-hydrophosphonylation of p-quinone methides using water as a green solvent. The reaction showed broad scope with excellent functional group tolerance. The practicability of this method was demonstrated by carrying out the reaction on the gram scale whereby product was obtained in high yield by the filtration technique avoiding chromatographic purification.

Cp*Ir(III)-Catalyzed C-H/O-H Functionalization of Salicylaldehydes for the Synthesis of Chromones at Room Temperature.

Herein, we report Cp*Ir(III)-catalyzed C-H/O-H-bond functionalization of salicylaldehydes with α-diazocarbonyl compounds for the synthesis of chromones under redox-neutral conditions. The reaction proceeds at room temperature and displays excellent functional group tolerance along with high yields of the corresponding products. The developed reaction protocol was successfully applied for the late-stage functionalization of estrone derivative.

Cp*Ir(iii)-catalyzed C-H/N-H functionalization of sulfoximines for the synthesis of 1,2-benzothiazines at room temperature.

The first Cp*Ir(iii)-catalyzed C-H/N-H bond functionalization of sulfoximines with α-diazocarbonyl compounds has been developed for the synthesis of 1,2-benzothiazines under redox-neutral conditions. The reactions proceed at room temperature with excellent functional group tolerance and high yields without the requirement of any silver additive.