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.

Reverse Regioselective Cp*Co(III)-Catalyzed [4 + 2] C-H Annulation of N-Chloroamides with Vinylsilanes: Synthesis of 4-Silylated Isoquinolones and Their Synthetic Utilities.

We have developed a Cp*Co(III)-catalyzed reverse regioselective [4 + 2] annulation of N-chlorobenzamides/acrylamides with vinylsilanes for the synthesis of 4-silylated isoquinolones. The reaction was performed at ambient temperature under redox-neutral conditions. The reaction utilized the N-Cl bond as an internal oxidant, furnished the required products with excellent regioselectivities, and demonstrated high functional group tolerance. The synthetic utility of 4-silylated isoquinolones has been demonstrated for the preparation of 4-heteroarylated and 4-alkylated isoquinolones via metal-free C-C couplings. Additionally, 3,4-dihydroisoquinolones were synthesized via protodesilylation of 4-silylated isoquinolones, thus making vinylsilane an ethylene surrogate.

Redox-neutral C-H annulation strategies for the synthesis of heterocycles via high-valent Cp*Co(III) catalysis.

A variety of biologically active molecules, pharmaceuticals, and natural products consist of a nitrogen-containing heterocyclic backbone. The majority of them are isoquinolones, indoles, isoquinolines, etc.; thereby the synthesis and derivatization of such heterocycles are synthetically very relevant. Also, certain naphthol derivatives have high synthetic utility as agrochemicals and in dye industries. Previous approaches have utilized ruthenium, rhodium, or iridium which may not be desirable due to the high toxicity, low abundance, and high cost of such 4d and 5d metals. Moreover, the need for an external oxidant during the reaction also adds by-products to the system. A high-valent cobalt-catalyzed redox-neutral C-H functionalization strategy has emerged to be a far better alternative in this regard. The use of the non-noble metal cobalt allows for selectivity and specificity in product formation. Also, the redox-neutral concept avoids the use of an external oxidant either due to the presence of a metal in a non-variable oxidation state throughout the catalytic cycle or due to the presence of an oxidizing directing group or an oxidizing coupling partner. Such an oxidizing directing group not only directs the catalyst to a specific reaction site by chelation but also regenerates the catalyst at the end of the cycle. Certain bonds such as N-O, N-N, N-Cl, N-S, and C-S are the main game-players behind the oxidizing property of such directing groups. In the other case, the directing group only chelates the catalyst to a reaction center, whereas the oxidation is carried out by the upcoming group/coupling partner. Overall, merging the redox-neutral concept with the high-valent cobalt catalysis is paving the way forward toward a sustainable and environmentally friendly approach. This review critically describes the mechanistic understanding, scope, limitations, and synthesis of various biologically relevant heterocycles via the redox-neutral concept in the high-valent Cp*Co(III)-catalyzed C-H functionalization chemistry domain.