The present review is devoted to summarizing the recent advances (2015–2017) in the field of metal-catalysed group-directed C–H functionalisation.

Joined forces: Alcohol dehydrogenase, enoate reductase, and Baeyer–Villiger monooxygenase are combined in a cascade reaction by coexpression in E. coli to have a recombinant whole‐cell biocatalyst. Such an artificial metabolic “mini”‐pathway provides access to functionalized chiral compounds in high yields and optical purities as exemplified for kinetic resolutions, desymmetrizations, and regiodivergent biotransformations.

Chemoenzymatic one‐pot processes based on the combination of metal catalysis and biocatalysis open up highly attractive perspectives regarding the production of enantiopure compounds. By combining a gold‐catalyzed hydration reaction with an enzymatic reduction, we present a straightforward and atom‐economical chemoenzymatic method for the synthesis of secondary alcohols with excellent optical purity. Efficient cofactor recycling exploits the solvent of the metal‐catalyzed step as an auxiliary substrate for the enzymatic step.

We present a concurrent chemo/biocatalytic one pot reaction cascade by combining a metal (Pd/Cu) assisted Liebeskind–Srogl coupling with an enantioselective enzymatic reduction for the production of chiral amines and alcohols.

Alkynylation reactions of N-protected tetrahydroisoquinolines have been performed using several different protocols of cross dehydrogenative coupling. Initially, a CuCl-catalyzed method was investigated, which worked well with three different N-protecting groups, namely phenyl, PMP, and benzyl and t-BuOOH as oxidant in acetonitrile as solvent. The peroxide could then be replaced by simple air and acetonitrile for water, leading to an overall very environmentally friendly protocol. Finally, a decarboxylative alkynylation protocol starting from alkynoic acids was also developed using again air as oxidant. This avoids the use of gaseous alkynes in the introduction of short-chained alkyne substituents.Graphical abstract