From pirates and killers: does metabolite diversity drive bacterial competition?
This article discusses interspecies competition by sets of closely related metabolites with significantly different biological activities.
Catalytic carbene/alkyne metathesis (CAM): a versatile strategy for alkyne bifunctionalization
Cascade reactions involving a catalytic carbene/alkyne metathesis (CAM) process through a vinyl carbene intermediate provide an efficient and step-economic approach for the construction of polycyclic frameworks with structural diversity.
The catalytic Mitsunobu reaction: a critical analysis of the current state-of-the-art
This Review article provides a summary and critical metrics-based analysis of recently developed catalytic Mitsunobu reactions.
Progress in the synthesis of fluorinated phosphatidylcholines for biological applications
Fluorinated phospholipids have attracted a lot of interest over the past 40 years. While mono- and polyfluorinated analogs are mostly designed to be used as 19F NMR probes, highly fluorinated phospholipids are mainly developed as drug delivery devices and oxygen carriers. This review describes their synthetic pathways, their properties and potential applications.
Transient imines as ‘next generation’ directing groups for the catalytic functionalisation of C–H bonds in a single operation
This review describes recent developments in the use of catalytic transient directing groups, through imine linkages, which in combination with transition metal catalysts provide streamlined C–H functionalisation processes.
Review of synthetic approaches toward maoecrystal V
Synthetic approaches toward the complex natural product diterpenoid maoecrystal V are reviewed, including successful total syntheses, published synthetic efforts, and efforts compiled from dissertations.
Chiral proton-transfer shuttle catalysts for carbene insertion reactions
The development of chiral proton-transfer shuttles provides a totally new enantiocontrol strategy for transition metal-catalyzed asymmetric carbene insertion reactions.
The Piancatelli reaction and its variants: recent applications to high added-value chemicals and biomass valorization
The conversion of furfuryl alcohols by the Piancatelli reaction (and its C- and N-variants) provided highly functionalized cyclopentenones (intermolecular) and spirocycles (intramolecular).
Catalytic asymmetric enamine protonation reaction
Recent advances in catalytic enantioselective enamine protonation for the synthesis of optically active carbonyl compounds are summarized in this review.
Aldehydes can switch the chemoselectivity of electrophiles in protein labeling
The derivatization of an electrophile can switch its chemoselectivity. The aldehyde-conjugated epoxide and sulfonate ester provide the proof of principle and deliver N-terminus tagged proteins.
StnK2 catalysing a Pictet–Spengler reaction involved in the biosynthesis of the antitumor reagent streptonigrin
StnK2 is a new Pictet–Spenglerase specifically catalyzing a (1R,3S,4S)-tetrahydro-β-carboline scaffold as the biosynthetic intermediate of the antitumor reagent streptonigrin.
Superelectrophilic activation of 1-nitronaphthalene in the presence of aluminum chloride. Reactions with benzene and cyclohexane
Aluminum chloride was successfully used instead of liquid superacids to mediate selective reactions of 1-nitronaphthalene with benzene and cyclohexane.
Chiral isoxazolidine-mediated stereoselective umpolung α-phenylation of methyl ketones
Asymmetric nucleophilic phenylation of N-alkoxyenamine with triphenylaluminium is achieved for the formation of enantioenriched α-phenyl ketones through a one-pot process.
Stapling of two PEGylated side chains increases the conformational stability of the WW domain via an entropic effect
PEGylation + stapling contributes more to conformational stability when the two linked sites are close in tertiary structure but far apart in primary sequence.
Rh-Catalyzed aminative dearomatization of 2-naphthols
β-Naphthalenones bearing a naked α-amino group could be rapidly constructed through a Rh-catalyzed aminative dearomatization reaction of 2-naphthols with O-(2,4-dinitrophenyl)hydroxylamine.
Sodium carbonate promoted [3 + 2] annulation of α-halohydroxamates and isocyanates
Access to hydantoin cores via a [3 + 2] annulation of α-halohydroxamates and isocyanates involving aza-oxyallyl cations.
Regioselective [3 + 2]-annulation of hydrazonyl chlorides with 1,3-dicarbonyl compounds for assembling of polysubstituted pyrazoles
The facile approach to polysubstituted pyrazoles from hydrazonyl chlorides and 1,3-dicarbonyl compounds has been developed. Hydrazonyl chlorides reacted with N-phenyl-3-oxobutanamides smoothly to afford a series of polysubstituted pyrazoles in 67–98% yields via the [3 + 2]-cycloaddition.
Fluorogenic “photoclick” labelling of DNA using a Cy3 dye
Two 2′-deoxyuridines as new building blocks for automated DNA synthesis carry a small aryltetrazole as a “photoclickable” group at their 5-positions.
A pendant peptide endows a sunscreen with water-resistance
A small-molecule UV-filter with a pendant collagen mimetic peptide anneals to a collagen-laden surface and protects against UV radiation.
Preparation of homoallylic amines via a three-component coupling process
A three-component synthesis of homoallylic amines is described.
Two-step activity-based protein profiling of diacylglycerol lipase
Diacylglycerol lipases (DAGL) produce the endocannabinoid 2-arachidonoylglycerol, a key modulator of neurotransmitter release.
Deletion of a global regulator LaeB leads to the discovery of novel polyketides in Aspergillus nidulans
By disruption of LaeB, a global regulator recently characterized in Aspergillus nidulans, eight cryptic compounds in the mutant were identified, including seven polyketides and one NRPS-like product.
Electrochemical Hofmann rearrangement mediated by NaBr: practical access to bioactive carbamates
An electrochemical Hofmann rearrangement is reported, which provides general and practical access to bioactive carbamates.
Chiral NHC-catalyzed 1,3-dipolar [3 + 2] cycloaddition of azomethine imines with α-chloroaldehydes for the synthesis of bicyclic pyrazolidinones
An NHC-catalyzed [3 + 2] cycloaddition reaction of azomethine imines and α-chloroaldehydes was developed for the synthesis of chiral bicyclic pyrazolidinone derivatives.
Tuning the fluorescence of tetraphenylethylene in dilute solutions via modulating multiple-hydrogen-bonding interactions between a Hamilton receptor and cyanuric acid
A hydrogen bonded luminescent supramolecular network from HTPE and CTPE can be further tuned.
Synthesis of the [7-5-5] tricyclic core of Daphniphyllum alkaloids
The [7-5-5] tricyclic core of the Daphniphyllum alkaloids was constructed, featuring a Claisen-Ireland rearrangement to install the two contiguous stereogenic centers, E1cB elimination to form the tetrasubstituted C–C double bond, and a 2,3-Wittig rearrangement to construct the quaternary carbon.
In vivo and in vitro identification of Z-BOX C – a new bilirubin oxidation end product
A new bilirubin degradation end product was isolated and characterized.
A concise total synthesis of cochlearoid B
A T-type calcium channel inhibiting natural product cochlearoid B was synthesized in 7 linear steps.
Anion transport by ortho-phenylene bis-ureas across cell and vesicle membranes
These simple bis-ureas are found to be powerful anionophores in synthetic vesicles, and also in a live cell assay employing yellow fluorescent protein.
Organocatalytic enantioselective synthesis of acyclic pyrimidine nucleosides by aza-Michael reaction
Organocatalytic enantioselective synthesis of acyclic pyrimidine nucleosides was achieved by the aza-Michael reaction of pyrimidines as N-centered nucleophiles to α,β-unsaturated aldehydes.
Syntheses and in vitro biological evaluation of S1PR1 ligands and PET studies of four F-18 labeled radiotracers in the brain of nonhuman primates
Four potent and selective F-18 labeled S1PR1 radiotracers were radiosynthesized and three of them were able to cross blood–brain-barrier and enter into the brain of nonhuman primates.
pH-Rate profiles establish that polyketide synthase dehydratase domains utilize a single-base mechanism
PKS dehydratases utilize a one-base mechanism.
New tetralactam hosts for squaraine dyes
Tetralactam macrocycles with similar substituents (methyl, methoxy, methylenedioxy) on the macrocycle aromatic sidewalls have very different squaraine recognition properties.
Nazarov cyclisations initiated by DDQ-oxidised pentadienyl ether: a mechanistic investigation from the DFT perspective
The rate determining step for such a Nazarov cyclization is direct hydride transfer from pentadienyl ether to the oxygen of DDQ.
Aerobic oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid and its derivatives by heterogeneous NHC-catalysis
Heterogeneous NHC-catalysis is an effective synthetic platform for the production of bio-based furan derivatives.
Synthesis and mass spectrometric analysis of disaccharides from methanolysis of heparan sulfate
Heparan sulfate (HS) disaccharides were synthesized to identify HS methanolysis products by LC-MS/MS with applications for mucopolysaccharidosis disorders.
Synthesis and application of a highly branched, mechanism-based 2-deoxy-2-fluoro-oligosaccharide inhibitor of endo-xyloglucanases
Xyloglucan (XyG) is a complex polysaccharide that is ubiquitous and often abundant in the cell walls of terrestrial plants.
Origins of the enantioselectivity of a palladium catalyst with BINOL–phosphoric acid ligands
The enantioselectivity of the studied C–H activation is related to the Brønsted acidity and isopropyl groups of the effective catalysts.
Bimodal fluorogenic sensing of matrix proteolytic signatures in lung cancer
We present a highly-specific, rapidly activatable dual-FRET-smartprobe for the independent optical detection of metalloproteinases and thrombin in lung cancer tissue.
A novel peptide conformation: the γ-bend ribbon
Conformational analysis of oligopeptides based on the repeating –(S)-(αMe)Aze-(S)-Ala– dyad allowed the characterization of a 3D-structure featuring multiple, non-consecutive γ-bends.
Synthesis of highly rigid phosphine–oxazoline ligands for palladium-catalyzed asymmetric allylic alkylation
Rigid phosphine–oxazoline ligands with a spirocarbon stereogenic center were developed, which exhibited excellent catalytic performance for Pd-catalyzed allylic alkylation reactions.
Studies toward the synthesis of strevertenes A and G: stereoselective construction of C1–C19 segments of the molecules
Efficient route for the stereoselective synthesis of common C1–C19 segment of strevertenes A and G has been developed.
Dirhodium(II)/P(t-Bu)3 catalyzed tandem reaction of α,β-unsaturated aldehydes with arylboronic acids
Axially alkylphosphane ligated Rh2(OAc)4 catalyzes the tandem reaction of α,β-unsaturated aldehydes with arylboronic acids to produce ketone derivatives in high yields.
Stereoselective synthesis of 1,3-disubstituted dihydroisoquinolines viaL-phenylalanine-derived dihydroisoquinoline N-oxides
Addition of Grignard reagents and alkenes to readily available (S)-3-(hydroxymethyl)-3,4-dihydroisoquinoline-2-oxide allow the highly stereoselective synthesis of a range of 1,3-disubstituted tetrahydroisoquinolines.
Synthesis of difluoromethylated enynes by the reaction of α-(trifluoromethyl)styrenes with terminal alkynes
A novel and efficient method for the synthesis of difluoromethylated enynes by the reaction of α-(trifluoromethyl)styrenes with terminal alkynes with the assistance of NaOtBu was developed.
Dimericursones A and B: two unprecedented hexacyclic dimeric diterpenoids from the root barks of Jatropha curcas
Two unprecedented hexacyclic dimeric diterpenoids from Jatropha curcas and 2 showed significant NO inhibitory activity with IC50 values of 5.65 μM.
Toward the total synthesis of patellazole B: synthesis of an advanced C1–C25 fragment corresponding to the macrocyclic skeleton
A modular and highly convergent approach enables the assembly of an advanced intermediate towards the total synthesis of patellazole B – a promising anticancer agent.
tert-Butyl nitrite mediated nitrogen transfer reactions: synthesis of benzotriazoles and azides at room temperature
A conversion of o-phenylenediamines into benzotriazoles is reported with tert-butyl nitrite at room temperature. The optimized condition is also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides.
First catalyst-free CO2 trapping of N-acyliminium ions under ambient conditions: sustainable multicomponent synthesis of thia- and oxazolidinyl carbamates
A sustainable multicomponent approach through catalyst-free utilization of carbon dioxide under ambient conditions for the preparation of carbamates is reported.
Azodicarboxylate-free esterification with triphenylphosphine mediated by flavin and visible light: method development and stereoselectivity control
Photoredox catalysis: A new way to induce triphenylphosphine to be able to mediate nucleophilic substitution reactions of alcohols and acids.
Switching a regular tryptophan C4-prenyltransferase to a reverse tryptophan-containing cyclic dipeptide C3-prenyltransferase by sequential site-directed mutagenesis
The site-directed mutagenesis of FgaPT2 switches a regular C4-prenylation to a reverse C3-prenylation of tryptophan-containing cyclic dipeptides.
Stereoselective synthesis of 2,6-trans-4-oxopiperidines using an acid-mediated 6-endo-trig cyclisation
An acid-mediated 6-endo-trig cyclisation has been developed for the synthesis of trans-6-alkyl-2-methyl-4-oxopiperidines and used for the stereoselective preparation of quinolizidine alkaloid, (+)-myrtine and the piperidine alkaloid, (−)-solenopsin A.
Tracking down protein–protein interactions via a FRET-system using site-specific thiol-labeling
A novel Cys-specific bioorthogonalized linker was synthesized and applied in combination with bioorthogonally applicable fluorescent markers to track down protein–protein (p38-MK2) interactions by FRET.
Divergent biosynthesis of indole alkaloids FR900452 and spiro-maremycins
FR900452 was demonstrated to be biosynthesized by the gene cluster of maremycin G and diversified by SnoaL-like protein MarP.
Peripheral cyclic β-amino acids balance the stability and edge-protection of β-sandwiches
cis-2-Aminocyclohexanecarboxylic acid replacements at the edges of β-sandwiches reduce β-sheet propensities just enough to prevent aggregation but still maintain a compact structure.
Synthetic antibody protein mimics of infliximab by molecular scaffolding on novel CycloTriVeratrilene (CTV) derivatives
Downsizing of antibodies: molecular construction of chemo-synthetic antibodies of infliximab by scaffolding of three CDR loops yields synthetic antibodies binding hTNFα.
Synthesis of substituted piperidines by enantioselective desymmetrizing intramolecular aza-Michael reactions
An organocatalytic enantioselective intramolecular aza-Michael reaction has been described for the first time in a desymmetrization process employing substrates different from cyclohexadienones.
Diastereo- and enantioselective Mannich/cyclization cascade reaction of isocyanoacetates with cyclic sulfamide ketimines by cinchona alkaloid squaramide/AgOAc cooperative catalysis
This reaction provides facile access to a variety of optically active imidazoline-fused sulfahydantoin derivatives in excellent yields and good to excellent stereoselectivities.
Hypermonins A and B, two 6-norpolyprenylated acylphloroglucinols with unprecedented skeletons from Hypericum monogynum
Hypermonins A and B, two novel 6-norpolycyclic polyprenylated acylphloroglucinols (PPAPs), were isolated from the leaves and twigs of Hypericum monogynum.
Dynamic kinetic resolution of biaryl atropisomers by chiral dialkylaminopyridine catalysts
Dynamic kinetic resolutions of atropisomers using chiral DMAPs with fluxional chirality.
Expanding antibiotic chemical space around the nidulin pharmacophore
Reinvestigating antibiotic scaffolds that were identified during the Golden Age of antibiotic discovery, but have long since been “forgotten”, has proven to be an effective strategy for delivering next-generation antibiotics capable of combatting multidrug-resistant superbugs.
Synthesis of plasmodione metabolites and 13C-enriched plasmodione as chemical tools for drug metabolism investigation
A 10-step synthesis of the antimalarial lead, 13C18-enriched plasmodione, and of seven putative metabolites is described.
Synthetic polyprenol-pyrophosphate linked oligosaccharides are efficient substrates for mycobacterial galactan biosynthetic enzymes
Synthetic glycosyl polyprenol phosphates are substrates for enzymes required for cell wall assembly in mycobacteria, including the organism that causes tuberculosis.
High efficiency two-photon uncaging coupled by the correction of spontaneous hydrolysis
DNI-Glu proved to be several times more efficient, than MNI-Glu and other analogues.
Asymmetric synthesis of trans-4,5-disubstituted γ-butyrolactones involving a key allylboration step. First access to (−)-nicotlactone B and (−)-galbacin
A new approach based on one-pot sequential transformations with application for the first total synthesis of (−)-nicotlactone B and (−)-galbacin.
An efficient synthesis of 16H-dibenzo[2,3:6,7][1,4]oxazepino[5,4-b]quinazolin-16-ones via an Ullmann reaction catalyzed by CuI
16H-Dibenzo[2,3:6,7][1,4]oxazepino[5,4-b]quinazolin-16-ones were obtained from the available reactants 2-amino-N-(2-hydroxyphenyl)benzamide and 2-bromobenzaldehyde via an Ullmann reaction catalyzed by CuI.
Small-molecule anticancer agents kill cancer cells by harnessing reactive oxygen species in an iron-dependent manner
In the course of generating a library of open-chain epothilones, we discovered a new class of small molecule anticancer agents that has no effect on tubulin but instead kills selected cancer cell lines by harnessing reactive oxygen species in an iron-dependent manner.
Supramolecular chiroptical switching of helical-sense preferences through the two-way intramolecular transmission of a single chiral source
Complexation-induced reversal of helical-sense preferences is demonstrated with a simple molecule with a pair of exciton-coupled chromophores.
E–Z isomerization in Suzuki cross-couplings of haloenones: ligand effects and evidence for a separate catalytic cycle
We present evidence for a palladocyclic enolate-like pathway for isomerization of enones occurring during Suzuki cross-coupling reactions.
Nickel-catalyzed cross-coupling of β-carbonyl alkenyl pivalates with arylzinc chlorides
The reaction of β-carbonyl alkenyl pivalates with arylzinc reagents was carried out via nickel-catalyzed C–O bond cleavage, forming 3-aryl-substituted α,β-unsaturated carbonyl compounds in moderate to excellent yields.
About this collection
This on-going collection features all the articles published in Organic & Biomolecular Chemistry in 2018 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!