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Principles of quantum interference can guide the design of chromophores that undergo singlet fission. Now, ‘pencil and paper’ graphical models can be used to understand and predict the dynamics of triplet pairs generated through singlet fission in bridged dimers.
Asymmetric systems for catalytic carbohydrate functionalization are mostly limited to chiral copper complexes and organocatalysts. Now, a synergistic chiral Rh(I)- and organoboron-catalysed site-selective functionalization of carbohydrate polyols has been developed, giving stereocontrolled access to biologically relevant arylhydronaphthalene glycosides. Enantio-, diastereo-, regio- and anomeric control and dynamic kinetic resolution were found to be concomitantly operative.
Heteroatom–heteroatom cross-couplings have so far remained elusive. Now, a copper-catalysed enantioselective S–O cross-coupling of diverse diols or triols with sulfonyl chlorides has been realized via a single-electron reductive elimination manifold. The reaction provides access to value-added chiral C3 building blocks and inositol phosphates through enantioselective desymmetrization of biomass-derived alcohols.
Macrocyclic peptides can be genetically encoded and synthesized in cells; however, the programmable diversity is limited. Now, macrocycles containing two non-canonical amino acids have been genetically encoded and synthesized in codon-reassigned Syn61Δ3 cells. Incorporating diverse hydroxy acids in Syn61Δ3 cells enables the synthesis of non-natural depsipeptides containing either one or two ester bonds.
The enantioselective functionalization of C60 is highly challenging, typically requiring complex chiral tethers or demanding chromatography. Fullerenes have now been shown to undergo Diels–Alder reactions in a chemo-, regio- and enantio-selective fashion through confinement within an enantiopure metal–organic cage functionalized with a chiral formylpyridine group.
Aromaticity is a ubiquitous concept in organic chemistry yet it is less widespread for inorganic species. Now the cluster [(CpRu)3Bi6]–, obtained as part of a soluble salt, has been shown to exhibit aromatic behaviour referred to as φ-type, owing to a highly regular {Bi6} substructure causing a non-localizable molecular orbital of \(f_{z^3}\)-like symmetry.
The nitrogen reduction reaction is an extremely valuable but energy-intensive process. Now, a coordination polymer based on a [Zn–N2–Zn] unit has been shown to promote the formation of ammonia under ambient conditions by a photocatalytic reaction. The N2 moieties within the framework are reduced, creating unsaturated [Zn2+···Zn+] intermediates that are able to capture external N2 and sustain the cycle.
The transition state, a transient species where bond transformation occurs, fundamentally controls reaction dynamics. This important species can be probed through the photodetachment of an anionic precursor, as has now been shown in the F + NH3 reaction. A combination of theory and experiment reveals resonances that span the transition state.
The strong regiochemical preferences of electrophilic aromatic substitution have played a key role in defining the diversity of accessible chemical space. Now, it has been shown that the electrophilic arylation of phenols can be achieved at the electronically disfavoured meta-position via a formal 1,2-migration of a key σ-complex intermediate.
Direct oxidative methods for the enantioselective synthesis of heterobiaryl compounds that exhibit axial chirality remain elusive. Now, the use of an iron catalyst in the presence of a chiral PyBOX ligand and an oxidant enables the direct coupling of naphthols and indoles with high levels of enantio- and cross-selectivity.
Enzymes with identical sequences of amino acids can display varying activities when encoded with mRNA with different properties, but why this is the case has been a mystery. Now, it has been shown that synonymous mutations in mRNA alter the partitioning of proteins into long-lived soluble misfolded states with varying activities.
Photoactivation of EDA complexes was previously limited to electronically biased partners to secure productive charge-transfer interactions. Now, the participation of triarylsulfonium salts—formed by selective C–H sulfenylation—in photoactive EDA complexes with catalytic triarylamine donors provides a site-selective and metal-free strategy for the generation of aryl radicals and the formal C–H functionalization of native arenes.
Interlocked shape-persistent organic cages are rare structures and the majority are formed using π-stacking as the driving force. Now it is shown that weak dispersion interactions—which are modulated by changing the 1,4-substituents of the constituent dialdehyde linkers—can be used to form interlocked dimeric and trimeric catenated cages.
The synthesis of cyclic polymers remains challenging. Now a trifunctional B-P-B frustrated Lewis pair has been shown to enable easy access to cyclic acrylic polymers through a bimolecular mechanism. These cyclic polymers have enhanced thermodynamic properties compared with their linear counterparts, while maintaining high chemical recyclability.
Polyketide natural products often contain common repeat motifs that are synthesized using iterative processes. Now a masked 1,3-diol motif, generated by a two-step process based on boronic ester homologation, has enabled the efficient iterative synthesis of polyacetates, including bahamaolide A. In addition to oxidation, the 1,3-polyboronic esters were shown to undergo various stereospecific transformations.
Inelastic hydrogen atom scattering from surfaces provides a good benchmark for the validity of the Born–Oppenheimer approximation in surface chemistry. Now it has been shown that hydrogen atoms colliding with a semiconductor surface can efficiently excite electrons above the surface bandgap, representing a clear example of the failure of the approximation.
Modulation of surface properties and functions can be achieved through covalent and non-covalent molecular binding, but the lack of responsiveness and requirement for specific binding groups makes spatiotemporal control challenging. Now, it has been shown that adaptive insertion of a hydrophobic anchor into a poly(ethylene glycol) host is an effective non-covalent binding strategy for programmable surface functionalization.
Methods to access organofluorine compounds with a trifluoromethyl- and fluoro-substituted carbon stereogenic centre are severely limited. Now, a flexible and stereodivergent approach has been developed for the efficient preparation of homoallylic alcohols containing this moiety. Conversion to polyfluoro furanosides and pyranosides has been demonstrated, which is relevant to antiviral drug development.
The facile release of corrosive HCl gas and plasticizers from poly(vinyl chloride) (PVC) makes it a challenging material to recycle. Now, it has been shown that PVC waste can be directly used as a halogen source to synthesize chloroarenes. This paired electro(de)chlorination is mediated by a phthalate plasticizer already contained in PVC waste.
Expanding the biocatalysis toolbox for C–N bond formation is of great value. Now, a biocatalytic amination strategy using a new-to-nature mechanism involving nitrogen-centred radicals has been developed. The transformations are enabled by synergistic photoenzymatic catalysis, providing intra- and intermolecular hydroamination products with high yields and levels of enantioselectivity.