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P-centered ring-opening of quaternary phosphirenium salts (QPrS) predominantly leads to hydrophosphorylated products, while the C-centered ring-opening results mainly in the formation of phosphorus-containing cyclization products. Here the authors synthesize β-functionalized vinylphosphine oxides by the P addition of QPrS intermediates generated in situ.

Chemoselective reactions of two or multiple functional groups with similar reactivities remain an ongoing challenge in chemistry. Here the authors disclosed a chemoselective reaction of enedial and observed that the high chemoselectivity is mainly controlled via redox (rather than steric) properties of the substrate/catalyst.

Phthalidyl esters, commonly used prodrug moieties, are mostly prepared as a racemate. Here, the authors report an N-heterocylcic carbene-catalysed enantioselective acetalization of carboxylic acids and dialdehydes to give phthalidyl esters in high yields with good enantioselectivity.

Macrolactones exhibit distinct conformational and configurational properties and are widely found in natural products but catalysts to govern both macrolactone formation and stereochemical control remain largely unexplored. Here, the authors disclose an N-heterocyclic carbene (NHC)-catalyzed enantioselective synthesis of chiral macrolactones varying in ring size from sixteen to twenty members that feature distinct configurationally stable planar stereogenicity.

Conformational isomerization of organic molecules can be guided by noncovalent interactions. Here, the authors report the synthesis of chiral sulfoxides catalyzed by N-heterocyclic carbenes; intramolecular chalcogen bonding interactions are key for conformational locking.

Activation of C–C bonds is a powerful method for directly functionalizing organic molecules, but is still a challenging task. Here, the authors show that N-heterocyclic carbenes can activate the C–C bonds in cyclic ketones, allowing the enantioselective formation of lactams.

Combining metal catalysis and organocatalysis can be difficult, especially when dealing with strongly coordinating organic compounds such as N-heterocyclic carbenes. Here, the authors combine copper and N-heterocyclic carbene catalysis for the generation of ketimines and their use in stereoselective reactions.

Benzyl bromides can be activated for radical reactions by photocatalytic single electron transfer. Here the authors show thatN-heterocyclic carbenes are also capable of activating this pathway for nitrobenzyl bromides, and that the radical intermediates can add to the carbonyl group of ketones.

The benzene unit is a common scaffold in natural products and appears in most best selling drugs. Here, the authors report the efficient synthesis of substituted benzenes through a carbene-catalyzed formal [3+3] reaction, which does not require a pre-existing aromatic ring.

Selective functionalization of aromatic compounds is important in synthetic chemistry. Here the authors report anN-heterocyclic carbene-catalysed approach for enantioselectively converting ortho-hydroxyaldehydes to cyclic products, via activation of both phenol and aldehyde groups.

Cationic polymers conventionally kill bacteria via physical membrane disruptions. Here, the authors report the development of carbon acid cationic polymers that show potent activity against multidrug-resistant strains in murine infection models and prevent bovine mastitis, and present evidence that these polymers translocate across bacterial membrane aided by N-heterocyclic carbene.

The site-selective acylation of saccharides without extensive pre-protection of alcohol units has been a longstanding objective in organic synthesis. Here, the authors demonstrate that by simply altering the chirality of N-heterocyclic carbene (NHC) organic catalysts, the site-selectivity of saccharide acylation can be effectively modulated.

The use of heteroatom-centered anions as super-electron-donors (SEDs) for direct single-electron-transfer reactions has rarely been studied. Here, the authors show that heteroatom anions can be applied as SEDs to initiate radical reactions for synthesis of 3-substituted benzofurans, which have applications in both organic synthesis and pesticide development.

The search for efficient methods for the enantioselective synthesis of cyano-containing molecules is important but synthesis methods are often limited by the need of toxic cyano salts or reduction with hydrogen gas. Here the authors report the efficient and selective access to β-cyano carboxylic esters which can be easily converted into γ-aminobutyric acid derivatives with high optical purities.

Combined N-heterocyclic carbene and photoredox-catalysed strategies for the acylation of arenes offer regiocontrol that is complementary to Lewis-acid-mediated Friedel–Crafts approaches.

The authors report the synthesis of an enantiomeric block co-beta-peptide that kills methicillin-resistant Staphylococcus aureus, including biofilm and persister bacterial cells, and disperses biofilms. The copolymer displays antibacterial activity in human ex vivo and mouse in vivo infection models without toxicity.

Nitriles have proven to be useful functional groups in pharmaceuticals and polymers, both as active moieties themselves or as easy precursors to further transformations, but synthesis of benzonitriles with axial chirality has often been difficult. Here the authors make axially chiral benzonitriles via N-heterocyclic carbene organocatalysis via a dynamic kinetic resolution process.

Axially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Here the authors present a method to form axially chiral styrenes bearing sulfones and carboxylic acids via NHC catalysis.

The combination of carbene- and photocatalysis has enabled unorthodox routes to ketone syntheses, but usually requires engineered or activated substrates. Herein the authors present a carbene- and photocatalytic decarboxylative radical coupling of carboxylic acids and acyl imidazoles, in which the carboxylic acids are directly used as radical precursors.

Indole oxidation represents a fundamental organic transformation delivering valuable nitrogen compounds. Here, the authors report a general halide catalysis protocol applied to three classes of oxidation reactions of indoles with oxone as a sustainable terminal oxidant.

Direct β-carbon activation of saturated carbonyl compounds represents a significant fundamental challenge in organic chemistry. Here, the catalytic activation of saturated ester β-sp³ carbon as nucleophile via N-heterocyclic carbene organocatalysis is reported. The catalytically generated nucleophilic β-carbon undergoes enantioselective reactions with various electrophiles.