Articles in 2017

A squaramide-based anion transporter has now been shown to cause changes in the lysosomal pH leading to impairment of lysosomal enzyme activity and disruption of autophagic processes. The study provides the first experimental evidence that synthetic ion transporters can both disrupt autophagy and induce apoptosis.

Amidation is one of the most widely utilized organic reactions for the synthesis of pharmaceuticals and functional materials. DATB, characterized by the B₃NO₂ heterocycle, proved to act as a superb catalyst for the direct amidation with a distinct mechanistic pathway, displaying broadened applicability to a wide range of substrates.

A cytocompatible controlled radical polymerization method has now been developed that initiates polymer synthesis directly on the surface of living cells. This method achieves significantly enhanced polymer grafting and enables active manipulation of cellular phenotypes.

A programmable model of membraneless organelles comprised of intrinsically disordered proteins (IDPs) containing sequences of low complexity has now been developed. The rules governing the assembly of archetypal IDPs into biologically inspired mixed, layered and size-controlled configurations provides a new means for understanding intracellular phase behaviour of IDPs.

A chiral ammonium salt mediates a dynamic kinetic resolution of racemic α-aryl ketones by atropselective O-alkylation. Oxidation with DDQ gives access to C₂-symmetric and non-symmetric BINOL derivatives in high yields and with high enantioselectivity.

Mono-iron hydrogenase promotes the heterolytic cleavage of H₂ and subsequent hydride transfer to its organic substrate, H₄MPT⁺, which serves as a CO₂ ‘carrier’ in methanogenic pathways. Now, using an anthracene-scaffold-based approach, a synthetic model featuring enzyme-like Fe-C,N,S facial coordination has been developed. The model complex enables the bidirectional activity of H₂ activation and evolution.

The first example of an asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes has been described with trifluoromethyl aryl sulfonate as a new trifluoromethoxylation reagent. This reaction is operationally simple, scalable and proceeds under mild reaction conditions, which can be applied to the late-stage trifluoromethoxylation of complex small molecules.

The synthesis of well-defined planar polymers presents a significant challenge for chemists seeking to investigate their potential for use in emerging technologies. Now, a two-dimensional conjugated aromatic polymer has been synthesized via endogenous solid-state polymerization of pre-arranged monomers, and its performance as an organic anode in an ambient temperature sodium cell tested.

The construction of diversified compound libraries from identical substrates is attractive but remains a challenge in asymmetric synthesis. Here, we demonstrate switchable regioselective [6+2], [4+2] or [2+2] cycloadditions with α′-alkylidene-2-cyclopentenones via mild aminocatalysis, producing a spectrum of chiral frameworks with high structural diversity and molecular complexity.

2-aminothiazole — a hybrid of prebiotic amino acid and nucleotide precursors — sequentially accumulates and purifies glycolaldehyde and glyceraldehyde from complex mixtures in the order required for ribonucleotide synthesis, dynamically resolves glyceraldehyde from its ketose-isomer dihydroxyacetone, and provides the first strategy to select natural amino acids from abiotic aldehydes and ketones.

Understanding how oxygen-evolution reaction (OER) catalysts work is important for the development of efficient energy storage technologies. It has now been shown that lattice oxygen participates in O₂ generation during the OER on some highly active metal oxides and that this behaviour becomes more prevalent with greater metal–oxygen covalency.

NaO^tBu — an alkoxide salt — enables simple access to low-oxidation-state catalysis using sustainable first-row transition metals (Fe, Co, Mn, Ni). The approach works across a wide range of reductive alkene and alkyne functionlization reactions including hydroboration, hydrosilylation, hydrogenation, hydrovinylation and [2π+2π] cyclization reactions.