Themed collection 2021 Organic & Biomolecular Chemistry HOT article collection
Light-induced borylation: developments and mechanistic insights
This perspective delineates light-induced borylation methodologies, which have been developed in the last 10 years. Mechanistic insights have been explored throughout the article for these UV- and visible-light-induced borylation reactions.
Chemical probes targeting the kinase CK2: a journey outside the catalytic box
An up-to-date and comprehensive review on chemical probes targeting the important kinase CK2.
Phosphorus containing porous organic polymers: synthetic techniques and applications in organic synthesis and catalysis
This review features the recent advancement made in phosphorus-containing POPs, highlighting different synthetic techniques for their preparation and application in organic synthesis.
Approaches for peptide and protein cyclisation
Polypeptide cyclisation can enhance thermal stability, proteolytic resistance and membrane permeability. Cyclisation can be achieved by methods including chemical, enzyme and protein tag approaches. Each has strengths and limitations.
Modelling biocompatible ionic liquids based on organic acids and amino acids: challenges for computational models and future perspectives
From isolated molecules to the bulk phase: building models of biocompatible ionic liquids.
Recent advances in the synthesis and reactivity of azetidines: strain-driven character of the four-membered heterocycle
Azetidines represent one of the most important four-membered heterocycles in organic synthesis. We provide an overview of the synthesis, reactivity and application of azetidines with a focus on the most recent advances, trends and future directions.
α,β-Unsaturated acyl ammonium species as reactive intermediates in organocatalysis: an update
α,β-Unsaturated acyl ammonium species are versatile intermediates that have been applied in a variety of transformations including Michael additions, domino reactions and cycloadditions.
Aromatic Cope rearrangements
This review summarizes the ∼40 papers dating back to 1956 on the aromatic Cope rearrangement, and highlights the need for further studies, development, and applications of this transformation in synthesis.
The role of intermolecular forces in ionic reactions: the solvent effect, ion-pairing, aggregates and structured environment
A general view of the medium effects on ionic reactions involves the solvent effect, ion pairing, formation of aggregates and structured environment.
Recent advances in single-benzene-based fluorophores: physicochemical properties and applications
The recently reported physicochemical properties and applications of single-benzene-based fluorophores (SBBFs) are summarized.
Recent advances in the synthesis of α-amino ketones
This review on α-amino ketone synthesis collates and evaluates developments made in this area over the past decade, with an extended discussion on functional group compatibility, resultant product substitution patterns, and medicinal applications.
Beyond osmium: progress in 1,2-amino oxygenation of alkenes, 1,3-dienes, alkynes, and allenes
Olefin 1,2-difunctionalization is a popular synthetic strategy for synthesis of vicinal amino alcohols and their derivatives. This comprehensive review covers methods developed beyond the pioneering osmium-catalyzed Sharpless amino hydroxylation.
Reframing primary alkyl amines as aliphatic building blocks
This review covers recent and historical aliphatic deaminative functionalization reactions to encourage the use of primary amines as aliphatic building blocks.
Integrating abiotic chemical catalysis and enzymatic catalysis in living cells
We review hybrid systems of abiotic catalysis and enzymatic catalysis, which function in living cells. This research direction will stimulate multidisciplinary fields, including complex molecule synthesis, energy production, and life science.
Asymmetric bis(oxazoline)–Ni(II) catalyzed α-hydroxylation of cyclic β-keto esters under visible light
Driven by light, a highly enantioselective α-hydroxylation of β-keto esters catalyzed by bis(oxazoline)–Ni(acac)2 complexes under an O2 atmosphere has been developed.
Water binding stabilizes stacked conformations of ferrocene containing sheet-like aromatic oligoamides
The encapsulation of discrete water molecules in flexible sheet-like aromatic oligoamide foldamers, as evidenced by structural and spectroscopic studies, stabilizes their structure.
Plasma induced acceleration and selectivity in strain-promoted azide–alkyne cycloadditions
We report the unexpected acceleration of strain-promoted azide–alkyne cycloaddition in human plasma compared to classical solvent systems. Besides fast kinetics, human plasma also allows for discrimination between two azides in competition reaction.
Cu(I)-Catalyzed asymmetric exo-selective synthesis of substituted pyrrolidines via a 1,3-dipolar cycloaddition reaction
An efficient chiral metal complex catalysed asymmetric 1,3-dipolar cycloaddition reaction was developed to synthesize highly functionalised exo-pyrrolidines.
One-pot multi-step cascade protocols toward β-indolyl sulfoximidoyl amides via intermolecular trapping of an α-indolylpalladium complex by CO
Various β-indolyl sulfoximidoyl amides were efficiently prepared from ortho-iodoanilines, propargyl bromides, 1 atm of CO, and NH-sulfoximines, through a palladium-catalyzed indole annulation/carbonyl insertion/C–N bond formation cascade.
The copper-catalyzed selective monoalkylation of active methylene compounds with alkylsilyl peroxides
A novel method for a mild copper-catalyzed selective monoalkylation of active methylene compounds with various alkylsilyl peroxides has been developed.
Metal-free access to 3-allyl-2-alkoxychromanones via phosphine-catalyzed alkoxy allylation of chromones with MBH carbonates and alcohols
A phosphine-catalyzed alkoxy allylation of chromones with MBH carbonates and alcohols is established for the metal-free synthesis of 3-allyl-2-alkoxychromanones with high diastereoselectivity.
Direct and straightforward transfer of C1 functionalized synthons to phosphorous electrophiles for accessing gem-P-containing methanes
A modular strategy for preparing α-functionalized phosphorous-containing methyl-units.
Continuous flow as an enabling technology: a fast and versatile entry to functionalized glyoxal derivatives
Continuous Flow methods to access glyoxal derivatives, which serve as valuable precursors for heterocyclic chemistry.
Cyanoalkylation/alkynylation of allylic alcohol through intramolecular radical 1,2-alkynyl migration
A di-tert-butyl peroxide (DTBP)-promoted difunctionalization of α-aryl α-alkynyl allylic alcohols with alkyl nitriles was developed, affording a series of α-alkynyl γ-cyano functionalized ketones in moderate yields.
Investigating eosin Y as a photocatalyst for the radical-dependent activity-based probing of deubiquitinating enzymes
Assessment of the eosin Y initiated protein–protein thiol–ene reaction in a metal-free, oxygen-tolerant, visible-light mediated system.
Stereocontrolled syntheses of (−)- and (+)-γ-diisoeugenol along with optically active eight stereoisomers of 7,8′-epoxy-8,7′-neolignan
It was shown that reduction of the tertiary benzylic hydroxy group of 3-furanol followed by the intramolecular Friedel–Crafts reaction gave exclusively indane structure along with 7,8′-epoxy-8,7′-neolignan structure.
Copper-catalyzed one-pot amine-alkylation of quinones with amines and alkanes
Copper-catalyzed three-component amine-alkylation of quinones with amines and alkanes.
Development and application of a high throughput assay system for the detection of Rieske dioxygenase activity
A new periodate-based reactive assay system enables the rapid evaluation of the cis-dihydroxylation activity of Rieske dioxygenase enzymes.
Total synthesis of cynaropicrin
The first total synthesis of the sesquiterpene lactone cynaropicrin, isolated from artichoke, was achieved starting from (S)-α-pinene. The synthesis involved a stereoselective Favorskii rearrangement and a diastereoselective Barbier reaction.
An air-stable, Zn2+-based catalyst for hydrosilylation of alkenes and alkynes
An air-stable, Zn2+-based catalyst for catalytic hydrosilylation reactions of alkenes and alkynes.
Formation of amidino-borate derivatives by a multi-component reaction
Amidino-borate derivatives are formed in a five-component reaction between an olefin, three arylisocyanide equivalents and the dimethyl sulfide adduct of the bulky borane (Fmes)BH2.
Synthesis, structure and midkine binding of chondroitin sulfate oligosaccharide analogues
Chondroitin sulfate E mimetics displaying CH2OH groups instead of carboxylates retain the 3D structure and binding properties of natural sequences.
Switchable regioselective hydroalkylation of 2-arylindoles with maleimides
A condition-based switchable regioselective hydroalkylation of 2-arylindoles with maleimides has been developed.
Direct monitoring of biocatalytic deacetylation of amino acid substrates by 1H NMR reveals fine details of substrate specificity
A convenient NMR assay was used to monitor hydrolysis of a range of N-acyl-amino acids by an acylase biocatalyst.
The effect of deoxyfluorination and O-acylation on the cytotoxicity of N-acetyl-D-gluco- and D-galactosamine hemiacetals
Multiple deoxyfluorination of GlcNAc/GalNAc hemiacetals generated cytotoxic compounds.
Studies on a catalytic version of the Matteson asymmetric homologation reaction
Both Li and Yb complexes of a bis(oxazoline) ligand can induce asymmetry but the nature of Yb(OTf)3 is significant for its performance.
Ag(I)-Catalyzed rapid access to 2-amino-4-methylenethiazolines with potential applications in bioconjugation chemistry
An Ag(I)-catalyzed synthesis of 2-amino-4-methylenethiazolines from isothiocyanate and propargylamine was developed, and its implication in bioconjugation was examined.
HFIP-mediated 2-aza-Cope rearrangement: metal-free synthesis of α-substituted homoallylamines at ambient temperature
A synthesis of α-substituted homoallylamine derivatives is presented, involving the in situ generation of aldimines from readily available aldehydes and 1,1-diphenylhomoallylamines, followed by a 2-aza-Cope rearrangement in HFIP at room temperature.
Mechanistic studies of Cp*Ir(III)/Cp*Rh(III)-catalyzed branch-selective allylic C–H amidation: why is Cp*Ir(III) superior to Cp*Rh(III)?
DFT mechanistic investigations uncovered the origins of the reactivity and regioselectivity of Cp*Ir(III)/Cp*Rh(III)-catalyzed allylic C–H amidation reactions.
Electrochemical synthesis of sulfonated benzothiophenes using 2-alkynylthioanisoles and sodium sulfinates
Electrochemical sulfonylation/cyclization of 2-alkynylthioanisoles with sodium sulfinates was developed under catalyst-, external oxidant- and metal-free conditions.
Horeau amplification in the sequential acylative kinetic resolution of (±)-1,2-diols and (±)-1,3-diols in flow
The sequential kinetic resolution of (±)-1,2-syn and (±)-1,3-anti-diols in flow, using the polystyrene supported isothiourea, HyperBTM, gives highly enantioenriched products using the principles of Horeau amplification.
Palladium-catalyzed aerobic oxyarylthiolation of alkynone O-methyloximes with arylhydrazines and elemental sulfur
A novel and practical palladium-catalyzed aerobic oxyarylthiolation of alkynone O-methyloximes for the assembly of 4-sulfenylisoxazole derivatives is accomplished.
Pairing multicomponent stators with aromatic rotators for new emissive molecular rotors
Highly fluorescent molecular rotors sensitive to polarity changes were obtained through an Ugi–Sonogashira sequence.
Oxidative alkylation/alkynylation of terminal alkenes via alkylaldehyde decarbonylation and 1,2-alkynyl migration
Alkenes and alkylaldehydes offer a general access to the challenging quaternary carbon-containing but-3-yn-1-ones through decarbonylation and 1,2-alkynyl migration.
Concise catalytic asymmetric synthesis of (R)-4-amino Uhle's ketone
An efficient asymmetric synthesis of (R)-4-amino Uhle's ketone, a framework shared by most ergot alkaloids, was completed in five steps.
N-Alkenylation of hydroxamic acid derivatives with ethynyl benziodoxolone to synthesize cis-enamides through vinyl benziodoxolones
Ethynyl benziodoxolone enabled the chemoselective N-functionalization of O-alkyl hydroxamic acids derived from amino acids and pharmaceuticals. The synthesized cis-vinyl benziodoxolone was derivatized to hydroxamic acid-derived enamides.
Photocatalyst-free visible-light-promoted quinazolinone synthesis at room temperature utilizing aldehydes generated in situ via CC bond cleavage
This is the first report on a facile tandem route for synthesizing quinazolinones at room temperature from various aminobenzamides and in situ-generated aldehydes.
The mass spectrometric fragmentation mechanisms of catenulane and isocatenulane diterpenes
The EI-MS fragmentation mechanisms of three diterpenes from Catenulispora acidiphila and two semisynthetic derivatives were studied in extensive 13C-labelling experiments.
Nickel-catalyzed coupling of R2P(O)Me (R = aryl or alkoxy) with (hetero)arylmethyl alcohols
α-Alkylation of methyldiarylphosphine oxides and dialkyl methylphosphonates with (hetero)arylmethyl alcohols was performed under nickel catalysis.
Construction of fully substituted carbon centers containing a heteroatom and a CF3 group via in situ generated p-quinone methides
Facile and practical construction of heteroatom as well as CF3-containing fully substituted carbon centers was realized by 1,6-conjugate additions of a variety of heteronucleophiles to in situ generated δ-CF3-δ-substituted p-quinone methides.
Semisynthesis and biological evaluation of a focused library of unguinol derivatives as next-generation antibiotics
Semisynthetic unguinol derivatives showed potent activity against a panel of methicillin-resistant Staphylococcus aureus strains and are promising candidates for further development.
Ligand-free Suzuki–Miyaura cross-coupling with low Pd content: rapid development by a fluorescence-based high-throughput screening method
Highly efficient ligand-free Suzuki–Miyaura cross-coupling in aqueous solvent at room temperature was developed using metal oxides with low Pd content via a fluorescence-based high-throughput screening method.
A colorimetric sensor array for the classification of biologically relevant tri-, di- and mono-phosphates
A cyclic tetrapeptide paired with six commercially available indicators provides a chemosensing array able to classify biological phosphate derivatives.
A matrix targeted fluorescent probe to monitor mitochondrial dynamics
A far-red turn-on fluorescent probe (Mito-TG) with excellent biocompatibility, photostability, chemical stability targets mitochondrial matrix. The insensitivity of probe under different pH and ROS enabled tracking of mitophagy and Aβ induced mitochondrial dynamics.
Bifunctional metal–organic frameworks for the hydrogenation of nitrophenol using methanol as the hydrogen source
This work reports the reduction of 4-nitrophenol to 4-aminophenol using UiO-66(Zr) as a bifunctional photocatalyst and hydrogenation catalyst using methanol as the hydrogen source.
Kinetic and structure–activity studies of the triazolium ion-catalysed benzoin condensation
An initial rate evaluation of the triazolium-catalysed benzoin condensation permitted a Hammett structure–activity analysis providing insight into the rate-limiting step.
Quadruplex DNA-guided ligand selection from dynamic combinatorial libraries of acylhydrazones
Synthesis of dynamic combinatorial libraries of acylhydrazones in the presence of a G-quadruplex DNA template, followed by pull-down with streptavidin-coated magnetic beads, allows the identification of putative G-quadruplex binders.
Enantioselective N-heterocyclic carbene-catalysed intermolecular crossed benzoin condensations: improved catalyst design and the role of in situ racemisation
A N-heterocyclic carbene catalyst incorporating a bulky yet electron-deficient N-aryl substituent promotes chemoselective and enantioselective intermolecular crossed benzoin condensations.
One pot synthesis of thio-glycosides via aziridine opening reactions
thio-Glycosides with a pseudo-disaccharide structure are synthesized via aziridine opening reactions starting from glycosyl thioacetates with a one-pot protocol, which affords glycomimetics equipped for easy and stable conjugation to aglycones.
Two new seco-polycyclic polyprenylated acylphloroglucinol from Hypericum sampsonii
Two rare seco-polycyclic polyprenylated acylphloroglucinols (1 and 2) were isolated from Hypericum sampsonii. Compounds 1 and 2 showed moderate multidrug resistance (MDR) reversal activity to resistant cancer cells, HepG2/ADR and MCF-7/ADR.
Development of functionalized peptides for efficient inhibition of myostatin by selective photooxygenation
Functionalized peptides which consist of myostatin-binding peptide and on/off-switchable catalyst efficiently inhibit myostatin by selective photooxygenation, leading to a therapeutic strategy for muscular atrophic disorders.
DNAzymes for amine and peptide lysine acylation
In vitro selection identifies DNAzymes that acylate amino groups, including Lys in tethered peptides, and in some cases by transfer of a small glutaryl group.
About this collection
This on-going collection features all the articles published in Organic & Biomolecular Chemistry in 2021 that were highlighted by the reviewers of these articles as being interesting or having particularly significant research.
Congratulations to all the authors whose articles are featured!