Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain
the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in
Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles
and JavaScript.
Pyrroles are a common substructure in pharmaceuticals, materials and natural products. Now a multicomponent, titanium-catalysed synthesis of polysubstituted pyrroles — a nitrenoid analogue of the Pauson–Khand reaction — is reported. Stoichiometric and kinetic studies suggest that the reaction proceeds through an unusual TiII/TiIV redox cycle.
The functionalization of primary amines by C–H activation is often hindered by their strong metal-coordinating properties. Now, a steric tethering approach — which temporarily converts amino alcohols into hindered secondary amines — has been developed. The approach allows these amino alcohols to be transformed into structurally complex and diverse products using palladium-catalysed aliphatic C–H activation.
Although millions of zeolite structures have been predicted, only about 200 have been prepared over the past six decades. An assembly–disassembly–organization–reassembly process has now enabled the synthesis of two zeolites previously thought to be unfeasible, which have high framework energy and rare structural features such as odd-membered rings.
Singlet fission, a spin-allowed conversion of a spin-singlet state into a pair of spin-triplet excitons, may be useful for the development of next-generation photovoltaics. Ultrafast coherence measurements now show that vibrational motions play a critical role in fission as they facilitate the mixing of triplet-pair states with singlet excitons.
A concise synthesis of the fungal natural product epicolactone suggests that this highly stereochemically complex yet racemic natural product may come from a cascade reaction between two polyhydroxylated arenes.
Carl Wilhelm Scheele had a hand in the discovery of at least six elements and contributed to the early development of chemistry in numerous other ways. Bruce Gibb looks into Scheele's story and considers why he doesn't get the credit that he deserves.
Synthetic oligomers could potentially expand beyond the functions offered by proteins and nucleic acids. However, this requires precise methods for controlling their folding and self-assembly. Now, it is shown that two drastically different supramolecular architectures can be fabricated from closely related sequences using a single biomimetic scaffold.
C–H functionalization of organic compounds is an ideal yet challenging approach to organic synthesis. This Perspective covers the most recent developments concerning the palladium-catalysed norbornene-mediated C–H functionalization of arenes, including applications of these methodologies in natural products synthesis. Challenges as well as opportunities for future studies are also presented.
A vast number of possible isomers exist for each fullerene, yet few are observed experimentally. Neutral fullerenes typically minimize adjacent pentagons, but charged ones often tolerate them. Now, a simple model taking into account structural strain and π electronic aspects predicts the asymmetric relative stabilities of charged isomers.
Uncertainty associated with solution-based electron-transfer studies of DNA–metal-complex systems has now been overcome by combining X-ray and time-resolved infrared data obtained for ruthenium polypyridyl–DNA crystals. Using these methods both the geometry of the reaction site and the kinetics of the reversible photo-induced one-electron oxidation of guanine have been determined.
α-Substituted-β-hydroxy ketones are valuable intermediates, but their preparation by alkylation of enolates is difficult with hindered electrophiles. Now, a direct method for preparing α-substituted-β-hydroxy ketones — including those having α-quaternary centres — by addition of Grignard reagents to epoxyhydrazones has been developed, enabling the stereocontrolled incorporation of a wide range of carbon based substituents.
Oxynitrides are garnering interest because of their variety of novel properties, but their synthesis has typically involved highly reducing conditions that put significant constraints on their composition, structure and properties. Now, the lability of H− in perovskite oxyhydride BaTiO3−xHx has enabled H–/N3– exchange at a lower temperature, yielding a ferroelectric oxynitride BaTiO3−xN2x/3.
The stability of charged fullerenes is not as well understood as that of their neutral counterparts, with, for example, more frequent violations of the isolated-pentagon and pentagon-adjacency penalty rules. Now, a simple model based on the concepts of cage connectivity and frontier π orbitals predicts the relative stability of cationic and anionic fullerene isomers.
For many years, chemists have tried and failed to find efficient light-harvesting molecules based on Earth-abundant, environmentally friendly iron. Now, an iron complex has been developed with photoluminescent properties that are tuned to efficiently convert light to electrons.
Cross-couplings between boronic acids and halides are a mainstay of synthetic organic chemistry but enantioselective couplings are rare, and simply retaining the stereochemistry of the starting material is problematic. Now, it is shown that racemic allylic halides can converted to single enantiomer products by a rhodium(I)-catalysed asymmetric allylic arylation using arylboronic acids
Avoiding equal probability for clockwise and anticlockwise rotation is essential for the function of molecular motors, and both biological and synthetic systems take advantage of chirality to control the rotary direction. Now it has been shown, by integrating two rotor moieties in a symmetric meso motor design, that light-driven unidirectional rotary motion can be achieved in an achiral system.
O-linked N-acetyl-glucosamine (O-GlcNAc) has been identified as an endogenous modification of α-synuclein; however, its effect on the properties of the protein is unclear. Now, recombinant protein and synthetic peptides have been combined to produce both unmodified and site-specifically O-GlcNAc-modified α-synuclein. The O-GlcNAc modification at threonine 72 was shown to inhibit the aggregation and associated toxicity of α-synuclein.
Using iron instead of the scarce ruthenium in light-harvesting complexes is challenging because iron complexes generally have short-lived excited states. Now an iron complex has been developed that has a long-lived excited state, which can lead to photo-induced electron injection into nanoporous TiO2 with a yield of 92%.
A manganese catalyst is reported that aminates C–H bonds via a mechanism that lies between that of reactive noble metals (concerted) and chemoselective base metals (stepwise). Rather than exhibiting intermediate reactivity and selectivity, [Mn(tBuPc)] is an outlier, and aminates all C(sp3)–H bonds, including 1°, while remaining tolerant of oxidizable π-functionality.