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Controlling Product Selectivity by Modulating H-Bonding and the Rate of Hydrogen Elimination and Hydrogen Transfer
Srabani Nandi1, Sudipa Roy Mahapatra1, Isha Garg2
1Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, Uttar Pradesh (U.P.), India.
None:
Harnessing key intermediates in metal-catalyzed reactions enables highly selective organic transformations. Herein, we report an Ir(III)-catalyzed strategy for the selective synthesis of benzimidazoles and N-methylbenzimidazoles from diverse 2-nitroanilines and 1,2-diaminobenzenes using methanol. Solvent-controlled stabilization of the imine intermediate governed product selectivity: TFE favored benzimidazole formation, whereas methanol promoted rapid hydrogenation to N-methylbenzimidazoles. Mechanistic studies, supported by control experiments and DFT calculations, revealed the crucial role of solvent-modulated hydrogen transfer from a proton-responsive Ir-H species.
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