Themed collection Editor's choice - Paolo Melchiorre
Visual kinetic analysis
Naked-eye comparison of reaction profiles is a powerful tool to extract mechanistic information – FAQ, video tutorial and templated examples included.
Predictive and mechanistic multivariate linear regression models for reaction development
The utilization of physical organic molecular descriptors for the quantitative description of reaction outcomes in multivariate linear regression models is demonstrated as an effective tool for a priori prediction and mechanistic interrogation.
A transition-metal-free & diazo-free styrene cyclopropanation
A visible-light-enabled, operationally simple cyclopropanation reaction of styrenes with excellent functional group tolerance and chemoselectivity via carbenoid-like radicals.
Pd-catalyzed site-selective C(sp2)–H radical acylation of phenylalanine containing peptides with aldehydes
A novel Pd-catalyzed δ-C(sp2)–H functionalization reaction with readily available aldehydes towards the assembly of non-proteogenic acylated Phe-containing oligopeptides is presented.
Oxidant speciation and anionic ligand effects in the gold-catalyzed oxidative coupling of arenes and alkynes
The mechanism of the gold-catalyzed oxidative cross-coupling of arenes and alkynes has been studied in detail combining stoichiometric experiments with putative reaction intermediates and DFT calculations.
Bio-inspired synthesis of xishacorenes A, B, and C, and a new congener from fuscol
In this manuscript, we describe the conversion of fuscol, a natural product isolated in 1978, to xishacorenes A, B, and C, isolated in 2017, as well as a previously unreported congener, which we have named xishacorene D.
Oxidative organocatalysed enantioselective coupling of indoles with aldehydes that forms quaternary carbon stereocentres
The first organocatalysed, metal-free cross-nucleophile coupling of indoles with α-branched aldehydes forming acyclic stereoselective quaternary carbon centres is presented.
Catalytic asymmetric allylation of aldehydes with alkenes through allylic C(sp3)–H functionalization mediated by organophotoredox and chiral chromium hybrid catalysis
We have developed a catalytic asymmetric nucleophilic allylation of aldehydes using simple alkenes as pronucleophiles without relying on stoichiometric metals.
Catalytic radical difluoromethoxylation of arenes and heteroarenes
The first visible light photocatalytic generation and utilization of the OCF2H radical for direct (hetero)aryl C–H difluoromethoxylation at room temperature.
Synthesis of 18F-difluoromethylarenes using aryl boronic acids, ethyl bromofluoroacetate and [18F]fluoride
Herein, we report the radiosynthesis of 18F-difluoromethylarenes via the assembly of three components, a boron reagent, ethyl bromofluoroacetate, and cyclotron-produced non-carrier added [18F]fluoride.
A modular approach to prepare enantioenriched cyclobutanes: synthesis of (+)-rumphellaone A
A modular synthesis of enantioenriched polyfunctionalized cyclobutanes was developed and applied to the synthesis of (+)-rumphellaone A.
Photoredox-mediated remote C(sp3)–H heteroarylation of free alcohols
We report an efficient and economical method for remote δ C(sp3)–H heteroarylation of free aliphatic alcohols using a hypervalent iodine PFBI-OH oxidant under photoredox catalysis.
A quantitative reactivity scale for electrophilic fluorinating reagents
Through kinetic studies we provide a quantitative reactivity scale for ten electrophilic fluorination reagents.
Catalytic enantioselective radical coupling of activated ketones with N-aryl glycines
Asymmetric H-bonding catalysis as a viable strategy for enantioselective radical coupling of ketones is demonstrated.
Diastereoselective C–H carbonylative annulation of aliphatic amines: a rapid route to functionalized γ-lactams
A palladium(II)-catalysed C(sp3)–H carbonylation of free(NH) secondary aliphatic amines to 2-pyrrolidinones is described.
N-Heterocyclic carbenes as chiral Brønsted base catalysts: a highly diastereo- and enantioselective 1,6-addition reaction
Highly diastereo- and enantioselective 1,6-addition of β-keto amides to p-quinone methides catalyzed by N-heterocyclic carbenes via ion-pair interaction is developed.
Fine-tuned organic photoredox catalysts for fragmentation-alkynylation cascades of cyclic oxime ethers
Fine-tuned organic photoredox catalysts are introduced for the metal-free alkynylation of alkylnitrile radicals generated via oxidative ring opening of cyclic alkylketone oxime ethers.
Radical difluoromethylthiolation of aromatics enabled by visible light
A metal-catalyst-free and redox-neutral innate difluoromethylthiolation method enabled by visible light is described. This protocol employs a shelf-stable and readily available electrophilic difluoromethylthiolating reagent, PhSO2SCF2H, and converts a broad spectrum of arenes and heteroarenes to difluoromethylthioethers without noble metals and stoichiometric amount of additives.
Redox and photocatalytic properties of a NiII complex with a macrocyclic biquinazoline (Mabiq) ligand
Upon irradiation with visible light, the NiII complex 1 is converted to the reduced form 2 in the presence of NEt3. The Ni-based photosensitizer catalyzes the cyclization of a bromoalkyl-substituted indole.
Super electron donors derived from diboron
The combination of diboron, pyridine and base serves as an efficient source of structurally well-defined super electron donors.
About this collection
In 2019, Chemical Science welcomed Professor Paolo Melchiorre to the journal as an Associate Editor, handling papers in the areas of organic synthesis and catalysis, mainly utilising photochemical and radical reactivity patterns.
Paolo has looked back over recently published Chemical Science papers and has selected some outstanding articles on the theme of catalysis and synthetic methodology. We hope you enjoy reading through this selection.