Herein, we report a Co(III)-catalysed regioselective C8 linear olefination of isoquinoline-1H-2-one with terminal (aromatic and aliphatic) alkynes. This is an exclusive report for the C8 functionalization of isoquinolone using non-noble...

To detect the heavy metal toxicity by using self-assembled nanostructures a clathrin triskelion inspired highly functional C3-symmetric trimerized biotinylated di-tryptophan peptide was used. This triskelion peptide is known to be...

The recently developed palladium-catalyzed C-(sp 2 )−H olefination of 2-arylbenzaldehyde with the aid of a temporary directing group (TDG) via reversible imine formation delivers selective meta-C−H functionalization and possesses significant advantages over the well-established covalently attached directing group (DG) approach. In this report, a combined computational and experimental investigation has been performed to elucidate the detailed reaction mechanism and the origins of such remote meta-selectivity. The reaction proceeds in three major steps: C−H activation, 1,2-migratory insertion, and β-hydride elimination. While 1,2-migratory insertion of olefin is found to be the turnover-determining step, the selectivity is predetermined by the preceding C−H activation step. The computational observations have been corroborated along with experimentally conducted order determination studies, primary kinetic isotope effect (PKIE) study, and free energy correlation with Hammett plots. A temporary DG-bound Pd complex has been shown to be competent to promote meta-alkenylation. All the possible Pd-catalyzed template-directed C−H (ortho′, ortho, meta, para) olefinations of the 2-aryl benzaldehyde/aniline have been computationally investigated. The density functional theory (DFT)-based computations indicated that the other olefination reactions necessitate higher activation energy barriers compared with metaolefination. Distortion-interaction analysis (DIA), noncovalent interaction (NCI) analysis, and isodesmic studies were executed to unravel the mystery behind the origin of meta-regioselectivity.