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Nickel-Catalyzed C_sp2 -OMe Functionalization for Chemoselective Aromatic Homologation En Route to Nanographenes.

ABSTRACT: A Ni-catalyzed C_sp2 -OMe ortho-functionalization methodology to form chemoselectively alkyne monoannulation or aromatic homologation products is reported as a novel protocol towards the valorisation of substrates containing C_sp2 -OMe units. Double activation of C_sp2 -OMe and C_sp2 -F bonds is also demonstrated. Further use of aromatic homologation products towards the synthesis of nanographene-like compounds is described.

SUBMITTER: Capdevila L

PROVIDER: S-EPMC9321019 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The molecular functionalization of two-dimensional MoS2 is of practical relevance with a view to, for example, facilitating its liquid-phase processing or enhancing its performance in target applications. While derivatization of metallic 1T-phase MoS2 nanosheets has been relatively well studied, progress involving their thermodynamically stable, 2H-phase counterpart has been more limited due to the lower chemical reactivity of the latter. Here, we report a simple electrolytic strategy to functionalize 2H-phase MoS2 nanosheets with molecular groups derived from organoiodides. Upon cathodic treatment of a pre-expanded MoS2 crystal in an electrolyte containing the organoiodide, water-dispersible nanosheets derivatized with acetic acid or aniline moieties (∼0.10 molecular groups inserted per surface sulfur atom) were obtained. Analysis of the functionalization process indicated it to be enabled by the external supply of electrons from the cathodic potential, although they could also be sourced from a proper reducing agent, as well as by the presence of intrinsic defects in the 2H-phase MoS2 lattice (e.g., sulfur vacancies), where the molecular groups can bind. The acetic acid-functionalized nanosheets were tested as a non-noble metal-based catalyst for nitroarene and organic dye reduction, which is of practical utility in environmental remediation and chemical synthesis, and exhibited a markedly enhanced activity, surpassing that of other (1T- or 2H-phase) MoS2 materials and most non-noble metal catalysts previously reported for this application. The reduction kinetics (reaction order) was seen to correlate with the net electric charge of the nitroarene/dye molecules, which was ascribed to the distinct abilities of the latter to diffuse to the catalyst surface. The functionalized MoS2 catalyst also worked efficiently at realistic (i.e., high) reactant concentrations, as well as with binary and ternary mixtures of the reactants, and could be immobilized on a polymeric scaffold to expedite its manipulation and reuse.

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Nickel-Catalyzed C_sp2 -OMe Functionalization for Chemoselective Aromatic Homologation En Route to Nanographenes.

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OmicsDI is part of the ELIXIR infrastructure

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Dataset Information

Nickel-Catalyzed Csp2 -OMe Functionalization for Chemoselective Aromatic Homologation En Route to Nanographenes.

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OmicsDI is part of the ELIXIR infrastructure

Tweets

Nickel-Catalyzed C_sp2 -OMe Functionalization for Chemoselective Aromatic Homologation En Route to Nanographenes.