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Oxidation chemistry is critical to introducing molecular complexity during chemical synthesis. Development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Access to hypervalent iodine compounds — a class of broadly useful chemical oxidants — from O2 increases the scope of aerobic oxidation chemistry that can be achieved.
Although organocopper compounds are well known in organic chemistry, only recently has a set of catalytic reactions emerged that involve intermediates containing a copper-substituted stereogenic carbon centre. Now, a mechanistic study demonstrates that a better understanding of this distinction offers ways to address significant limitations in scope and enantioselectivity, explaining why unexpected variations in selectivity can occur.
The use of activating and directing groups can dramatically alter the course of a reaction. Now, it has been shown that an azo group can effectively perform as both in chiral phosphoric-acid catalysed formal nucleophilic aromatic substitution of azobenzene derivatives with indoles, affording axially chiral arylindoles with excellent enantioselectivities.
Steroids are arguably the most well studied and successful class of natural-product-inspired pharmaceuticals, yet step-economical and enantiospecific de novo synthesis remains challenging. Now, it is shown that the combination of metallacycle-mediated annulative cross-coupling and vinyl cyclopropane rearrangement chemistry can be used to deliver a variety of partially aromatic synthetic steroids in a concise, flexible and enantiospecific fashion.
DNA nanotechnology provides a versatile toolbox for engineering synthetic circuits in living cells. This Review discusses how nanostructures made from nucleic acids can enable biocomputation and also be readily interfaced with a variety of intracellular and in vivo components to facilitate synthetic biology applications.
DNA double helical structures are supramolecular assemblies that are typically held together by classical Watson–Crick pairing. Now, nucleotide chelation of silver ions supports an extended silver–DNA hybrid duplex featuring an uninterrupted silver array.
Water is increasingly recognized as being of paramount importance in biological processes, yet its exact role remains difficult to elucidate. Now, the motion of water molecules within and around a synthetic peptide-amphiphile nanofibre has been precisely determined, showing significant differences between its core and surface.
Ejecting electrons from negative ions using light can create structures that very closely resemble the transition states of bimolecular reactions. Now, using this technique, trapped quantum states, or 'resonances', have been observed in a seven-atom reaction, and theory has been shown to be up to the task of capturing such complex phenomena.
The question often arises as to who may have deserved a Nobel Prize but was not awarded one. Rarely is this discussion extended to who should have received more than one Nobel Prize, but in the field of organic synthesis there are some compelling candidates.
Glucose-responsive insulin is a therapeutic that modulates its potency, concentration or dosing relative to a patient’s dynamic glucose concentration. This Perspective summarizes some of the recent accomplishments in this field as well as discussing new computational algorithms that may aid in the development of such therapeutics.
Determining the structure–activity relationships for complex structures can be quite challenging, but it is often the method by which many natural products are optimized for use as drugs. Now, the combination of a fluoroaryl borane catalyst, a phosphine additive and a silane reducing agent enables the late-stage selective modification of complex bioactive natural products in order to provide rapid access to a wide array of structures, and therefore functions.
Rationally designed arrays of hydrogen bonds between aromatic oligoamide segments have now been shown to generate abiotic helix-turn-helix and unexpected dimeric and trimeric helix bundle motifs. These structures show kinetic and thermodynamic stability, and cooperative folding in nonpolar solvents.
The biosynthesis of secondary metabolites such as stephacidin A and its congeners continues to intrigue both biochemists and synthetic chemists. Now, a laboratory chemical synthesis of these natural products has been achieved based on a bioinspired synthetic strategy, which may provide key insights into the possible biosynthesis of these captivating molecules.
Providing detailed structural descriptions of the ultrafast photochemical events that occur in light-sensitive proteins is key to their understanding. Now, excited-state structures in the reversibly switchable fluorescent protein rsEGFP2 have been solved by time-resolved crystallography using an X-ray laser. These structures enabled the design of a mutant with improved photoswitching quantum yields.
A 335 base-pair gene encoding the green fluorescent protein iLOV and an epigenetically modified variant have now been assembled by click-DNA ligation of ten functionalized oligonucleotides. The resulting fully synthetic gene contained eight triazoles at the sites of chemical ligation, yet the synthetic gene was shown to be fully biocompatible in Escherichia coli.
Singlet fission — the conversion of one singlet exciton into two triplet excitons, could improve the efficiency of photovoltaic devices — but its mechanism is still to be fully understood. Now, in films of TIPS-tetracene, it has been shown that the formation of the triplet pair state, which has been proposed to mediate singlet fission, is ultrafast and vibronically coherent in this endothermic fission system.
Two important properties in an activated chemical reaction are the barrier height and its geometrical dependence. Now, a method has been developed to directly map the angle-dependent barrier to reaction from polarized scattering data for the Cl + CHD3 reaction. The method should be applicable to many other direct reactions with a colinear barrier.
Crystals are typically thought to be brittle and fragile materials, but needles of copper(II) acetylacetonate have now been shown to be flexible enough to be reversibly tied into a knot. Mechanistic investigations using synchrotron X-ray diffraction determined that the elastic bending occurs through rotation of the molecules within the crystal lattice.
The first new element produced after the Second World War has led a rather peaceful life since entering the period table — until it became the target of those producing superheavy elements, as Andreas Trabesinger describes.
