Co(III)-catalyzed alkenylation of 2-pyridones by using terminal alkyne as a reaction partner with high regioselectivity has been demonstrated for the first time. The reaction conditions are mild and compatible with a wide range of substrate combinations. It also shows good functional group tolerance. It proceeds through cyclometalation followed by alkyne insertion and protodemetalation steps. The formation of fiveand seven-membered cobaltacycle intermediates was also detected through highresolution mass spectrometry.

This review focuses on providing comprehensive highlights of the recent advances in the field of cobalt-catalysed C−H functionalization and related synthetic concepts relying on these through oxygen atom coordination. In...

Strain-driven palladium/N-heterocyclic carbene-catalyzed C–C bond activation of diphenylcyclopropenone (DPC) has been explored for one-step access to trisubstituted α,β-unsaturated esters and amides. The designed transformation works under mild conditions providing exclusively a single stereoisomer. Mechanistic studies support the oxidative addition of the C–C bond of cyclopropenone to in-situ-generated Pd(0) intermediate. We have proved that vinylic hydrogen in the product is coming from phenol/aniline through deuterium-labeling studies. Late-stage functionalization of bioactive molecules such as procaine, estrone, and hymecromone demonstrates the robustness of this protocol.

In recent years, transition metal-catalyzed strong C–C bond activation has significantly attracted the attention of synthetic chemists. This protocol enables simultaneous and direct functionalization of two different M–C bonds. Among different types of C–C bond activation strategies, strain-driven C–C bond activation has resulted in various otherwise difficult transformations. In this context, palladium catalyst has been extensively used and studied due to its robust reactivity and selectivity. Herein we have briefly discussed palladium-catalyzed C–C bond activation of three- and four-membered cycloalkane derivatives.

A new strategy for the C(7)-H functionalization of indoline derivatives using first-row transition-metal cobalt has been demonstrated wherein the pivaloyl group acts as a weakly coordinating directing group. Biologically important pyroquilon (tetrahydropyroquinolinone) derivatives have been synthesized in a one-pot manner through selective C(7)-H functionalization and concomitant cyclization. In this process, aromatic C−H and amidic C−N bonds are cleaved, and new C−C and C−N bonds are formed in a step-economical fashion. Further, selective C(7)-H alkenylation of indoline derivatives has also been accomplished using activated alkenes by varying the reaction conditions.Article pubs.acs.org/joc

A new application of hydroxylamine‐O‐sulfonic acid (HOSA) has been discovered whereby aromatic ketones react with HOSA and alkynes to form isoquinolines in the presence of a RhIII catalyst. This C–H/N–O annulation methodology gives excellent yields even without any silver additive, acid/base or metal oxidant. This is the first report wherein a directing group is simultaneously forming in situ, acting as acid additive, and also as an internal oxidant.

A Rh-catalyzed pot and step economic synthesis of aza-polycyclic aromatic hydrocarbons (N-PAHs) from readily available aryl ketones and alkynes has been disclosed. Additionally, a novel synthetic application of the well-known aminating reagent hydroxylamine-O-sulfonic acid (HOSA) has been explored as an in situ redox-neutral directing group for the formation of N-PAHs via isoquinoline. Multiple bond formation in a single operation through a cascade of triple C−H bond activations is the beauty of this protocol. The challenging annulations of two different alkynes in a regioselective fashion have been demonstrated effectively. Mechanistic studies reveal that 3,4-diphenyl-1-methylisoquinoline is an active intermediate for this one-pot transformation.

We report herein a cobalt-catalyzed 8-aminoquinoline-directed highly regio-and stereoselective C−H/N−H activation annulation of indole-2-carboxamides with 1,2-dihydronaphthalene for the synthesis of β-carboline-1-one derivatives at room temperature. A cheaper and commercially available cobalt catalyst has been used for this transformation. The protocol tolerates a wide range of functionalities, affording β-carboline-1-one derivatives in good yields. An initial mechanistic study revealed a reversible cyclometalation to be operative.