Deoxygenation of Ketones and α‐Ketoesters with a Bimetallic Iridium‐Molybdenum Catalyst

Abstract The selective reduction of ketones to the corresponding hydrocarbons is a fundamental transformation in organic synthesis with applications ranging from pharmaceuticals to biomass valorization. Traditional methods such as the Wolff–Kishner and Clemmensen reductions often face scalability challenges due to the use of harsh conditions and stoichiometric, often toxic reagents. Here, we report that bimetallic Ir‐Mo supported on SiO 2 is a highly efficient catalyst for the hydrodeoxygenation (HDO) of ketones using dihydrogen as a reductant, generating water as a sole byproduct. The catalyst, prepared from grafting Ir(COD)(DIA) (COD = 1,5‐cyclooctadiene, DIA = N,N’ ‐diisopropylacetamidinate) on a Mo‐doped SiO 2 support followed by reduction under H 2 , forms alloyed nanoparticles (2.0 nm) that exhibit very high selectivity for the deoxygenation of acetophenone derivatives, aliphatic ketones, and α‐ketoesters. The observed ring‐opening of cyclopropyl phenyl ketone and the formation of dimeric side products via carbonyl‐carbon coupling in acetophenones suggest the involvement of carbon‐centred radical intermediates. Overall, this work complements conventional methods, providing a more sustainable and versatile approach to ketone reduction in synthetic application.