-Alkanes to -alcohols: Formal primary C─H bond hydroxymethylation via quadruple relay catalysis.

Nature is able to synergistically combine multiple enzymes to conduct well-ordered biosynthetic transformations. Mimicking nature's multicatalysis in vitro may give rise to new chemical transformations via interplay of numerous molecular catalysts in one pot. The direct and selective conversion of abundant -alkanes to valuable -alcohols is a reaction with enormous potential applicability but has remained an unreached goal. Here, we show that a quadruple relay catalysis system involving three discrete transition metal catalysts enables selective synthesis of -alcohols via -alkane primary C─H bond hydroxymethylation. This one-pot multicatalysis system is composed of Ir-catalyzed alkane dehydrogenation, Rh-catalyzed olefin isomerization and hydroformylation, and Ru-catalyzed aldehyde hydrogenation. This system is further applied to synthesis of α,ω-diols from simple α-olefins through terminal-selective hydroxymethylation of silyl alkanes.