Recent Advances in C–H Activation for the Synthesis of π-Extended Materials

Abstract

The activation of typically unreactive aromatic C–H bonds by transition-metal catalysis has been receiving increased attention from the synthetic chemistry community in recent years. Advances in this area have enabled direct and site-selective modification of aromatic rings without the need for pre-functionalization. Accordingly, these techniques have found broad application in many fields, including the construction of extended π-systems for use in materials science. This review will discuss recent reports of C–H activation reactions applied toward the synthesis of π-extended functional materials.

Heterogenization of a Molecular Ni Catalyst within a Porous Macroligand for the Direct C–H Arylation of Heteroarenes

“…[3][4][5][6][7][8] The direct C-H arylation of heteroarenes is a key reaction for the synthesis of advanced heterobiaryls compounds. [9][10][11] In particular, the arylation of benzothiophene 12 is highly desirable because the (aryl)benzothiophene motif is widely present in active pharmaceutical ingredients (API) of marketed drugs [13][14][15] and in optoelectronic performance materials found in organic lightemitting diodes, organic field effect transistors and organic photovoltaic solar cells. [16][17][18][19] Moreover, the regioselective derivatization is of a paramount importance for structure-related activity.…”

Visible‐Light‐Induced Manganese‐Catalyzed Reactions: Present Approach and Future Prospects

“…The pathway of atom transfer in absence of external reductant has been demonstrated in the C−H functionalization of heteroarenes. C−H bond functionalization has evolved as a useful tool for the construction of various target molecules and thereby having a wide range of applications in the area of drug discovery to material science [30–33] . The unique ability to functionalize an otherwise inert C−H bond has captivated the researcher for years.…”

Harnessing sulfur and nitrogen in the cobalt(iii)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity

“…14 Such proximity-driven atomand step-efficient annulation strategies are synthetically valuable for the construction of natural and non-natural products, biologically important candidates, and molecules relevant to materials. [5][6] In spite of a broad synthetic versatility, these annulation methods forming CC, CN, and CO bonds are typically based on the use of precious 4d-and 5d-late transition metal-based catalysts (Rh, Ru, Pd, and Ir). 720 Meanwhile, the more abundant, relatively inexpensive and less toxic 3dTM cobalt complexes, such as Cp*Co(III)-type species, 2122 have emerged as attractive alternatives to the expensive Rh and Ir catalysts and have allowed to uncover mono-functionalization/cyclization processes involving unactivated arene CH bonds guided by a directing group (DG) ( Fig.…”