Iron and Cobalt Catalyzed Homogeneous Hydrofunctionalization of Carbonyl Compounds: Recent Advances and Mechanistic Insights

Abstract The hydrofunctionalization of carbonyl compounds via transition metal catalysis has become a versatile strategy in organic synthesis, allowing the efficient transformation of functional intermediates into valuable chemical products. Traditionally dominated by precious metals, this field has witnessed a growing interest in the development of rationally designed base‐metal complexes as alternative hydrofunctionalization catalysts. Among various catalysts explored, iron and cobalt‐complexes have demonstrated promising catalytic efficiency and sustainability. Recent progressions in the development of these iron and cobalt‐catalysts have broadened the scope and efficiency of the hydrofunctionalization transformations, offering sustainable and cost‐effective alternatives to traditional precious metal catalysts. This review provides a comprehensive overview of the recent developments in iron and cobalt‐catalyzed homogeneous hydroboration and hydrosilyaltion of carbonyl compounds (aldehydes and ketones) with an exclusive focus on the mechanistic insights behind these transformations. Addressing the advantages over conventional methods, it provides a profound discussion of the optimized reaction procedures, significance of distinct catalyst designs, activation modes, and the role of various ligand frameworks in facilitating the selective reduction of substrates. Furthermore, the existing inadequacies in establishing the mechanistic pathways and practical applicability in relevant industries are being discussed, alongside future directions for the development of more intricately designed, environmentally benign catalytic systems.