The making of mirror-image versions of naturally occurring cyclodextrins (CDs) is challenging and constitutes an untouched goal of the CD community. Now a concise approach is developed for the diastereoselective synthesis of three mirror-image CDs in an efficient and scalable manner.

Acid-triggered reversible addition–fragmentation chain-transfer polymerizations, in the absence of conventional initiating species and in the dark, are reported to prepare polymers with low dispersity and high end-group fidelity. The protonation of monomers catalyses both the initiation and propagation steps and can also be applied to free radical polymerizations.

The synthesis of high-nuclearity copper(I) nanoclusters remains challenging due to their low stability. Now four high-nuclearity Cu(I) nanoclusters have been successfully isolated by introducing a bifunctional phosphoramide ligand into the Cu/RC≡CH assembly system, enhancing complex stability through cooperative bonding.

Enzymatic C–Se bond forming reactions are rare. Now an enzymatic method for the synthesis of organoselenium compounds is reported using an ‘element engineering’ strategy. This method allows selenium analogues of cysteine, thiamine and a chuangxinmycin derivative to be produced using sulfur carrier proteins.

The isolation of secondary and primary carbon radical species is challenging, owing to their instability. Now the reduction of an acyclic bis(imino)carbene conjugate acid enables the isolation of a stable pentadienyl-type radical. In silico and in vitro probing of its properties reveal a propensity to act as a secondary carbon radical.

Biocatalytic methods for the synthesis of isoindolones, via C–H activation, have remained elusive. Now, an enantiodivergent artificial-metalloenzyme-catalysed method for the synthesis of chiral isoindolones is reported, using a streptavidin–biotin–Rh(III) catalyst system. Crystallographic analysis reveals the key residues that control stereoselectivity in streptavidin.

The in situ generation of reactive (di)gallenes from a gallium–fluorobenzene complex and commercial chiral and achiral bisphosphine ligands is presented. The Ga(I) complex cations can undergo reversible cycloadditions to 1-alkenes and bond insertions into H–Si and H–B bonds.

Development of fluorine rebound processes at an enzymatic Fe(III) centre are a challenge. Now, a plant-derived non-haem iron enzyme, 1-aminocyclopropane-1-carboxylic acid oxidase, is repurposed and evolved to catalyse chemo- and enantioselective C(sp³)–H fluorination, forming a range of enantioenriched organofluorine products.

A computationally guided approach was used to predict the hierarchical assembly of four trigonal-shaped organic cage compounds into a more symmetric, higher-order, tetrahedral-shaped ‘cage of cages’ that crystallizes into a porous superstructure.

Enantioselective triple [2 + 2 + 2] cycloadditions are reported that enable the synthesis of 3D π-extended carbo[11] and [13]helicenes, which show excellent circularly polarized luminescence brightness (up to 513 M⁻¹ cm⁻¹), the highest value among helicene derivatives.

Irreproducible synthetic methods consume time, money, and resources. Here, we highlight the steps Nature Synthesis takes to help authors make their synthetic procedures as reproducible as possible.