Recent advances in Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation via carbene migratory insertion

Abstract

The review highlighted diverse annulations, including nitrogen, oxygen, sulfur heterocycles and carbocylizations via Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation with various arene and carbene precursors.

Transition‐Metal‐Catalyzed C−H Bond Functionalization of Arenes/Heteroarenes via Tandem C−H Activation and Subsequent Carbene Migratory Insertion Strategy

“…possess such fused structures with ring-junction nitrogen atom. Hence, to corroborate the efforts of synthesizing such molecular scaffolds, Ellman and co-workers, in 2017, reported a Rh(III)-catalyzed synthesis of [5,6] bicyclic heterocycles (with ring junction À N atoms) via CÀ H activation of C-alkenyl azoles and their tandem coupling with α-diazo-β-ketoesters (Scheme 42c). [134] The reaction has been extended to alkenyl imidazoles, pyrazoles and triazoles to construct products with À N inclusion at different sites.…”

“…With due concern to heterocyclic compounds, [5,6]-fused heterocycles with the heteroatom at the ring junction have become increasingly prominent in medicinal chemistry owing to their electronic and shape-correlativity with adenine and guanine nucleobases. Many FDA-approved drugs like trazodone, zolpidem, zaleplon, etc.…”

“…[4a] Kanchupalli and co-workers, have detailed the recent advances in Rh(III)/Ir(III)-catalyzed CÀ H functionalization/annulation via carbene migratory insertion. [5] The same group has also recently reviewed the Co(III), Rh(III) & Ir(III)-catalyzed direct CÀ H alkylation/alkenylation/arylation with carbene precursors. [6] Liu and Zhang have focused upon the Au-catalyzed transformations of α-diazocarbonyl compounds, [7] whereas the reactivity of λ5-phosphorus-containing α-diazo compounds have been assessed by Marinozzi.…”

The Role of Sulphonamides and N‐Sulphonyl Ketimines/Aldimines as Directing Groups in the Field of C−H Activation

“…The carbenoid‐induced C−H functionalization reactions were far away from being synthetically useful [27–29] . Metal carbenoid behaves as a highly electrophilic species which is characterized by poor selectivity but on extensive efforts, these positive charges built up can be stabilized by atoms like N, O, etc [30] .…”

Rh(iii)-catalyzed synthesis of dibenzo[b,d]pyran-6-ones from aryl ketone O-acetyl oximes and quinones via C–H activation and C–C bond cleavage

“…In the past decade, transition-metal-catalyzed C–H bond activation has proven to be a powerful tool in organic syntheses 11 and several methods for the synthesis of dibenzo[ b , d ]pyran-6-ones via C–H activation have been reported. 12 Actually, in 2015, our group reported Rh( iii )-catalyzed synthesis of dibenzo[ b , d ]pyran-6-ones from N -methoxybenzamides and quinones through C–H activation annulation.…”