Divergent Synthesis of Ketones and Alcohols via Iron-Catalyzed Three-Component Alcohol Cross-Coupling.

Functionalized ketones and alcohols are two privileged scaffolds widely found in natural products and biologically active compounds. They are also key synthetic intermediates in target-oriented synthesis. The divergent synthesis of ketones and alcohols from the same starting materials and catalysts via the borrowing hydrogen (BH) reaction is of great significance. Despite the significant advances in the divergent two-component alcohol transformation, recent catalytic systems show weaknesses in the selective cross-coupling of multicomponent alcohols, which can easily produce highly functionalized molecules. New, inexpensive, and readily available Fe catalysts were synthesized and successfully used for the cross-coupling of multicomponent alcohols. By regulating the reaction conditions, we achieved the divergent synthesis of β,β-methylated/alkylated alcohols and α,α-methylated/alkylated ketones with high selectivity. The use of readily available starting materials, low catalyst loading, broad substrate scope, ease of scale-up, and versatile functionalizations of the products make this approach highly practical and attractive.