Volume 2 Issue 8, August 2023

Assembly and functionalization of biologically active steroids continue to pose a synthetic challenge. Now, mining and engineering of selective P450 C–H hydroxylases provide a biocatalytic C14–H hydroxylation, which can be integrated into chemoenzymatic syntheses of C14-functionalized steroids.

Metalloclusters play important roles in biology, materials and catalysis; however, their synthesis is not straightforward. Now, a strategy is reported where a controlled level of substitution based on incoming ligand steric properties is achieved, creating interesting metallocluster compositions.

A partial sequential galvanic exchange method is reported for synthesizing heterostructured interfaces between ordered intermetallic phases on a preformed metal template. Four distinct phases with engineered interfaces between them could be combined in one particle.

Renewable-energy-driven electrosynthesis of chemical feedstocks is gaining attention as a green alternative to traditional processes. Now, the production of industrially relevant C–S-based compounds from CO₂ and SO₃²⁻, with a simple Cu₂O electrocatalyst, has been demonstrated.

Chemoenzymatic strategies that combine chemical and enzymatic transformations are becoming increasingly popular in the synthesis of complex molecules. This Review highlights notable case studies in the application of chemoenzymatic strategies for structure–activity relationship explorations of bioactive natural products.

Controllable synthesis of 1D metal halide perovskite nanocrystals is challenging due to their structural symmetry and ionic crystal nature. Now, a general platform of cylindrical unimolecular nanoreactors has been developed to craft a variety of 1D perovskite nanorods with tailored dimensions and compositions.

C14-functionalized steroids are pharmaceutically valuable, but their synthesis is challenging. Now a chemoenzymatic route is reported featuring a key biocatalytic C14α-hydroxylation, enabled by protein engineering of a C14α-hydroxylase (CYP14A) from Cochliobolus lunatus. Dehydration and olefin functionalization of the biocatalytic reaction products provides C14-functionalized steroids.

Controlling the number and arrangement of ligands around metalloclusters is challenging. Now, a method for imparting site-differentiation to homoleptic clusters is reported in which the site-differentiation pattern is dictated by the steric profile of the incoming ligand.

The tailored synthesis of heterostructured intermetallic nanomaterials (iNMs) is challenging. Now, a galvanic replacement strategy is reported for the construction of a library of iNMs. Layered interfacial growth produces intermetallic heterostructures with controllable compositions, structures and interfaces.

Electrochemical routes to commodity chemicals are increasingly important to decarbonize the chemicals industry. Now, an electrochemical route to sulfonate products using CO₂ and SO₃²⁻ as building blocks has been reported, expanding the scope of electrochemical CO₂ reduction.

The selective functionalization of strong, neutral C(sp³)–H bonds, such as in alkanes, is synthetically challenging. Now, a transition-metal- and photosensitizer-free strategy employing allyl bromides as reagents and sodium fluoride as an activator has been developed for the selective C(sp³)–H functionalization of alkanes, cycloalkanes and other relatively unreactive molecules.

Ortho-C–H and meta-C–H functionalization of arenes is well developed; however, para-C–H functionalization is more challenging. Now, a method for the synthesis of para-functionalized anilides from arylhydroxylamines and O- and S-nucleophiles is reported. The process uses fluorosulfuryl imidazolium triflates at low temperature and probably comprises O-fluorosulfonation, followed by N–O bond cleavage and nucleophilic addition.

Controlling the self-assembly of large coordination cages is challenging owing to entropic costs and difficulties in error correction. Now an array of large cages prepared by the rational design of alterations that allow for the tuning of the dihedral angle between pentagonal subunits is reported.