Molecularly Engineering Defective Basal Planes in Molybdenum Sulfide for the Direct Synthesis of Benzimidazoles by Reductive Coupling of Dinitroarenes with Aldehydes

[EN] Developing more sustainable catalytic processes for preparing N-heterocyclic compounds in a less costly, compact, and greener manner from cheap and readily available reagents is highly desirable in modern synthetic chemistry. Herein, we report a straightforward synthesis of benzimidazoles by reductive coupling of o-dinitroarenes with aldehydes in the presence of molecular hydrogen. An innovative molecular cluster-based synthetic strategy that employs Mo3S4 complexes as precursors have been used to engineer a sulfur-deficient molybdenum disulfide (MoS2)-type material displaying structural defects on both the naturally occurring edge positions and along the typically inactive basal planes. By applying this catalyst, a broad range of functionalized 2-substituted benzimidazoles, including bioactive compounds, can be selectively synthesized by such a direct hydrogenative coupling protocol even in the presence of hydrogenation-sensitive functional groups, such as double and triple carbon-carbon bonds, nitrile and ester groups, and halogens as well as diverse types of heteroarenes. This work has been supported by the Gen-T Plan of the Generalitat Valenciana through the "Subvencions a l'Excel center dot le`ncia Cientifica de Ju ' niors Investigadors" program (SEJI/2020/018). Finantial support from the Spanish National Research Council (CSIC) is gratefully acknowledged (Project No. 201880E064). S.M. thanks for financial assistance from Ministerio de Ciencia e Innovacion from Spain and fondos FEDER in the framework of the project PID2019-105881RBI00 and DGA/fondos FEDER (construyendo Europa desde Aragon) for funding the research group Platon (E31_17R). M.R. and F.G. acknowledge the Vice-Rectorate for Research, Innovation and Transfer of the Universitat Polite`cnica de Vale`ncia (UPV) for a pre-and postdoctoral (PAID-10-20) fellowship, respectively. The authors also thank the Electron Microscopy Service of the UPV for TEM and STEM facilities and Dr. G. Antorrena for technical support in XPS studies. Rodenes-Carrillo, M.; Gonell-Gómez, F.; Martín, S.; Corma Canós, A.; Sorribes-Terrés, I. (2022). Molecularly Engineering Defective Basal Planes in Molybdenum Sulfide for the Direct Synthesis of Benzimidazoles by Reductive Coupling of Dinitroarenes with Aldehydes. JACS Au. 2(3):601-612. https://doi.org/10.1021/jacsau.1c00477