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 n-alkanes to valuable n-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 n-alcohols via n-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.

The asymmetric hydrogenation of vinylsilanes catalyzed by a new C 1-symmetric phosphine–pyridine–oxazoline cobalt complex is described. The method provides an efficient approach to chiral tertiary silanes with enantioselectivities up to 99% ee. Furthermore, the o-methyl-substituted benzylic silane products undergo ruthenium-catalyzed dehydrogenative silylation to produce chiral benzosilolanes in high yields without racemization of the stereogenic center α to the quaternary Si atom.

The dehydrogenation of abundant alkane feedstocks to olefins is one of the mostly intensively investigated reactions in organic catalysis. A long-standing, pervasive challenge in this transformation is the direct dehydrogenation of unactivated 1,1-disubstituted ethane, an aliphatic motif commonly found in organic molecules. Here, we report the design of a diphosphine chloroiridium catalyst for undirected dehydrogenation of this aliphatic class to form valuable 1,1-disubstituted ethylene. Featuring high site selectivity and excellent functional group compatibility, this catalytic system is applicable to late-stage dehydrogenation of complex bioactive molecules. Moreover, the system enables unprecedented dehydrogenation of polypropene with controllable degree of desaturation, dehydrogenating more than 10 in 100 propene units. Further derivatizations of the resulting double bonds afford functionalized polypropenes.