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Themed collection Mechanistic, computational & physical organic chemistry in OBC

158 items - Showing page 1 of 3
Review Article

A theoretical review for novel Lewis base amine/imine-catalyzed reactions

Recent advances in computational investigations of Lewis base amine/imine-catalyzed reactions have been systematically summarized and reviewed for the first time.

Graphical abstract: A theoretical review for novel Lewis base amine/imine-catalyzed reactions
Review Article

Optical purity, enantiomeric excess and the Horeau effect

Optical purity (op) and enantiomeric excess (ee) become equal when either heterochiral dimerization constant is twice that of homochiral dimerization constant or specific rotations of monomer and dimer are equal.

Graphical abstract: Optical purity, enantiomeric excess and the Horeau effect
Review Article

Synthetic and mechanistic aspects of sulfonyl migrations

Sulfonyl migrations, frequently described as ‘unusual’ or ‘unexpected’, from the last 20 years, including 1,2-, 1,3-, 1,4-, 1,5-, 1,6- and 1,7-sulfonyl shifts, through either radical or polar processes, either inter- or intramolecularly are reviewed.

Graphical abstract: Synthetic and mechanistic aspects of sulfonyl migrations
From the themed collection: Synthetic methodology in OBC
Review Article

Mechanistic knowledge and noncovalent interactions as the key features for enantioselective catalysed multicomponent reactions: a critical review

This critical short review focuses on some key features which determine successful enantioselective catalysed multicomponent reactions (MCRs) and are typically underappreciated in the literature.

Graphical abstract: Mechanistic knowledge and noncovalent interactions as the key features for enantioselective catalysed multicomponent reactions: a critical review
Review Article

The importance of N-heterocyclic carbene basicity in organocatalysis

This review highlights the importance of N-heterocyclic carbene (NHC) basicity for transformations in which NHCs are used as catalysts.

Graphical abstract: The importance of N-heterocyclic carbene basicity in organocatalysis
Communication

On the reciprocal relationship between σ-hole bonding and (anti)aromaticity gain in ketocyclopolyenes

σ-Hole bonding interactions (e.g., tetrel, pnictogen, chalcogen, and halogen bonding) can polarize π-electrons to enhance cyclic [4n] π-electron delocalization (i.e., antiaromaticity gain) or cyclic [4n + 2] π-electron delocalization (i.e., aromaticity gain).

Graphical abstract: On the reciprocal relationship between σ-hole bonding and (anti)aromaticity gain in ketocyclopolyenes
Communication

Divergent pathway and reactivity control of intramolecular arene C–H vinylation by vinyl cations

A computational study revealed the mechanistic details and controlling factors of reactivity in intramolecular C–H vinylation through a vinyl cation intermediate.

Graphical abstract: Divergent pathway and reactivity control of intramolecular arene C–H vinylation by vinyl cations
Communication

The optimal DFT approach in DP4 NMR structure analysis – pushing the limits of relative configuration elucidation

What computational methods should be used to achieve the most reliable result in computational structure elucidation? A study on the effect of quality and quantity of geometries on computational NMR structure elucidation performance is reported.

Graphical abstract: The optimal DFT approach in DP4 NMR structure analysis – pushing the limits of relative configuration elucidation
Communication

Mechanism of nitrones and allenoates cascade reactions for the synthesis of dihydro[1,2-a]indoles

Quantum mechanical calculations (DLPNO-CCSD(T) and M06-2X) are employed to gain insights into the mechanism and selectivity in the catalytic synthesis of dihydropyrido[1,2-a]indoles from the cascade reaction between nitrones and allenes.

Graphical abstract: Mechanism of nitrones and allenoates cascade reactions for the synthesis of dihydro[1,2-a]indoles
Communication

A Viedma ripening route to an enantiopure building block for Levetiracetam and Brivaracetam

A simple route to enantiomerically pure (S)-2-aminobutyramide – the chiral component of the anti-epileptic drugs Levetiracetam and Brivaracetam has been developed. This approach is based on the rational design and application of a Viedma ripening process. The practical potential of the process is demonstrated on a large scale.

Graphical abstract: A Viedma ripening route to an enantiopure building block for Levetiracetam and Brivaracetam
Communication

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.

Graphical abstract: Superelectrophilic activation of 1-nitronaphthalene in the presence of aluminum chloride. Reactions with benzene and cyclohexane
Communication

Experimental evidence for the formation of cationic intermediates during iodine(III)-mediated oxidative dearomatization of phenols

Hammett analysis reveals iodine(III)-mediated oxidative dearomatization reactions proceed through cationic intermediates and not direct nucleophilic attack on an activated phenol.

Graphical abstract: Experimental evidence for the formation of cationic intermediates during iodine(iii)-mediated oxidative dearomatization of phenols
Communication

On the dual reactivity of a Janus-type mesoionic dipole: experiments and theoretical validation

A mesoionic bicycle, easily synthesized from a proteinogenic amino acid, L-leucine, behaves as both thiazolium-olate and diazolium-olate dipoles, as unveiled by its dipolar cycloadditions.

Graphical abstract: On the dual reactivity of a Janus-type mesoionic dipole: experiments and theoretical validation
Communication

A “cross-stitched” peptide with improved helicity and proteolytic stability

Peptide “cross-stitching” maintains binding affinity and can enhance helical and proteolytic stability.

Graphical abstract: A “cross-stitched” peptide with improved helicity and proteolytic stability
Paper

A mechanistic study on Cu(I) catalyzed carboxylation of the C–F bond with CO2: a DFT study

Cu(I) catalyzed carboxylation of the C–F bond is an excellent method for construction of complex fluoroacrylate compounds with high regioselectivity. Here, theoretical calculations were carried out to investigate the detailed mechanism and origin of regioselectivity.

Graphical abstract: A mechanistic study on Cu(i) catalyzed carboxylation of the C–F bond with CO2: a DFT study
Accepted Manuscript - Paper

Regioselectivity in the adiabatic photocleavage of DNA-based oxetanes

Paper

Raise the anchor! Synthesis, X-ray and NMR characterization of 1,3,5-triazinanes with an axial tert-butyl group

N-t-Bu-N′,N′′-Disulfonamide-1,3,5-triazinanes were synthesized and studied by X-ray single crystal structure analysis and dynamic low-temperature NMR.

Graphical abstract: Raise the anchor! Synthesis, X-ray and NMR characterization of 1,3,5-triazinanes with an axial tert-butyl group
Paper

How the combination of PhIO and I2 provides a species responsible for conducting organic reactions through radical mechanisms

This contribution provides an answer to the long-standing question of how organic radicals are produced by the PhIO/I2 system and how the ensuing radicals are oxidized by the same system to yield the organic products.

Graphical abstract: How the combination of PhIO and I2 provides a species responsible for conducting organic reactions through radical mechanisms
Paper

Experimental and computational evidence on gold-catalyzed regioselective hydration of phthalimido-protected propargylamines: an entry to β-amino ketones

Gold-catalyzed regioselective hydration of phthalimido-protected propargylamines.

Graphical abstract: Experimental and computational evidence on gold-catalyzed regioselective hydration of phthalimido-protected propargylamines: an entry to β-amino ketones
Paper

Microwave-assisted nucleophilic degradation of organophosphorus pesticides in propylene carbonate

Degradation of organophosphorus pesticides was achieved by using microwaves, an ionic liquid and propylene carbonate.

Graphical abstract: Microwave-assisted nucleophilic degradation of organophosphorus pesticides in propylene carbonate
Paper

Guest-induced supramolecular chirality transfer in [2]pseudorotaxanes: experimental and computational study

We constructed several [2]pseudorotaxanes via chiral binaphthalene crown ethers and achiral ammonium salts, and found that the binaphthalene groups can induce new CD signals only in the [2]pseudorotaxane between the hosts and the guest with anthryl.

Graphical abstract: Guest-induced supramolecular chirality transfer in [2]pseudorotaxanes: experimental and computational study
Paper

How inverting β-1,4-galactosyltransferase-1 can quench a high charge of the by-product UDP3− in catalysis: a QM/MM study of enzymatic reaction with native and UDP-5′ thio galactose substrates

The function of Asp252 in the catalysis of β-1,4-galactosyltransferase-1 may be the stabilization of a high charge of the by-product UDP3− by a substrate-assisted proton transfer reaction.

Graphical abstract: How inverting β-1,4-galactosyltransferase-1 can quench a high charge of the by-product UDP3− in catalysis: a QM/MM study of enzymatic reaction with native and UDP-5′ thio galactose substrates
From the themed collection: Chemical biology in OBC
Paper

Influence of a 4′-substituent on the efficiency of flavonol-based fluorescent indicators of β-glycosidase activity

Fluorescent probes for glycosidases, based on the excited-state intramolecular proton transfer (ESIPT) phenomenon, are presented.

Graphical abstract: Influence of a 4′-substituent on the efficiency of flavonol-based fluorescent indicators of β-glycosidase activity
Paper

A simpler method affords evaluation of π stabilization by phenylalanine of several biochemical carbocations

Simple models based on measurements taken from X-ray structures of relevant active sites are used to evaluate π stabilization by phenylalanine of several biochemical carbocations.

Graphical abstract: A simpler method affords evaluation of π stabilization by phenylalanine of several biochemical carbocations
Paper

Computational investigations of NHC-backbone configurations for applications in organocatalytic umpolung reactions

Computational modeling and orbital analyses reveal enhanced catalytic properties based on N-heterocyclic carbene backbone modifications.

Graphical abstract: Computational investigations of NHC-backbone configurations for applications in organocatalytic umpolung reactions
Paper

The effect of bisimidazolium-based ionic liquids on a bimolecular substitution process. Are two head(group)s better than one?

Bisimidazolium-based ionic liquids generally result in greater rate constants than the corresponding monocationic salts. The effect depends on the length of the bridging chain; likely due to a change in the mode of interactions in solution.

Graphical abstract: The effect of bisimidazolium-based ionic liquids on a bimolecular substitution process. Are two head(group)s better than one?
Paper

Oxidative damage of proline residues by nitrate radicals (NO3˙): a kinetic and product study

Kinetic studies in acetonitrile revealed that proline residues in peptides are considerably protected against radical-induced oxidative damage by the neighbouring peptide bonds, compared with the single amino acid.

Graphical abstract: Oxidative damage of proline residues by nitrate radicals (NO3˙): a kinetic and product study
Paper

Deconvolution of fast exchange equilibrium states in NMR spectroscopy using virtual reference standards and probability theory

DFT–GIAO calculations combined with probability theory enable accurate prediction of fast exchange equilibrium states based on one experimental NMR dataset.

Graphical abstract: Deconvolution of fast exchange equilibrium states in NMR spectroscopy using virtual reference standards and probability theory
Paper

Mechanistic insights into Smiles rearrangement. Focus on π–π stacking interactions along the radical cascade

The synthesis of new arene and heteroarene scaffolds of therapeutic interest has generated a renewed interest in the domino radical cyclisation–Smiles.

Graphical abstract: Mechanistic insights into Smiles rearrangement. Focus on π–π stacking interactions along the radical cascade
Paper

Decomplexation as a rate limitation in the thiol-Michael addition of N-acrylamides

Experimental and computational agreement highlights rate-limiting “product decomplexation” and functional group effects in the thiol-Michael addition, utilized for sequence-defined oligomers.

Graphical abstract: Decomplexation as a rate limitation in the thiol-Michael addition of N-acrylamides
Paper

A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen

A metal-free oxidation of a mesoionic dipole with atmospheric oxygen triggers a complex cascade reaction through spin intercrossing, as supported by computation, and leading to polycycles with complete diastereoselection.

Graphical abstract: A fully diastereoselective oxidation of a mesoionic dipole with triplet molecular oxygen
Paper

The effect of solvation in torquoselectivity: ring opening of monosubstituted cyclobutenes

The paradigmatic electrocyclic ring opening of monosubstituted cyclobutenes has been used to diagnose possible solvation effects tuning the torquoselectivity observed in these reactions.

Graphical abstract: The effect of solvation in torquoselectivity: ring opening of monosubstituted cyclobutenes
Paper

Influence of phenylpropanoid units of lignin and its oxidized derivatives on the stability and βO4 binding properties: DFT and QTAIM approach

The interference of the phenylpropanoid units (S, G and H) on the properties of the βO4 bond was investigated by the topological analysis via QTAIM and the stability of the lignin and its oxidized structure were studied by the gap analysis

Graphical abstract: Influence of phenylpropanoid units of lignin and its oxidized derivatives on the stability and βO4 binding properties: DFT and QTAIM approach
Paper

The chemical gymnastics of enterocin: evidence for stereodivergence in Nature

Stereodivergence in Nature encapsulates both enzymatic (biosynthetic) and non-enzymatic (chemical) diversification of natural product scaffolds arising from a single biosynthetic pathway.

Graphical abstract: The chemical gymnastics of enterocin: evidence for stereodivergence in Nature
Paper

Palladium-catalyzed C–H activation of anisole with electron-deficient auxiliary ligands: a mechanistic investigation

In this work, the experimentally observed site-selectivity and ligand choice of Yu's meta-arylation reaction were rationalized through DFT calculations.

Graphical abstract: Palladium-catalyzed C–H activation of anisole with electron-deficient auxiliary ligands: a mechanistic investigation
Paper

Understanding the mechanism and reactivity of Pd-catalyzed C–P bond metathesis of aryl phosphines: a computational study

Computational study revealed the mechanistic details and reactivity profile of the Pd/PhI-cocatalyzed C–P bond metathesis of aryl phosphines.

Graphical abstract: Understanding the mechanism and reactivity of Pd-catalyzed C–P bond metathesis of aryl phosphines: a computational study
Paper

Monophenolase and catecholase activity of Aspergillus oryzae catechol oxidase: insights from hybrid QM/MM calculations

Monophenolase and diphenolase activities of the [Cu2O2]2+ active site of Aspergillus oryzae catechol oxidase are revealed by hybrid QM/MM calculations.

Graphical abstract: Monophenolase and catecholase activity of Aspergillus oryzae catechol oxidase: insights from hybrid QM/MM calculations
Paper

Photochemical [2 + 2] cycloaddition reaction of carbonyl compounds with Danishefsky diene

An efficient oxetane formation has been developed in the photochemical [2 + 2] cycloaddition reaction of benzophenone with Danishefsky diene.

Graphical abstract: Photochemical [2 + 2] cycloaddition reaction of carbonyl compounds with Danishefsky diene
Open Access Paper

Cross-linking of aromatic phenolate groups by cytochrome P450 enzymes: a model for the biosynthesis of vancomycin by OxyB

Aromatic cross-linking by cytochrome P450 enzymes was studied computationally. P450 Compound I rapidly abstracts two weak phenolic H-atoms that link up via a rate-determining C–O bond formation.

Graphical abstract: Cross-linking of aromatic phenolate groups by cytochrome P450 enzymes: a model for the biosynthesis of vancomycin by OxyB
Paper

Understanding the structures and aromaticity of heteroporphyrins with computations

Different heteroporphyrins go through two different aromatic pathways, either 18π-[18]annulene or 22π-electron model.

Graphical abstract: Understanding the structures and aromaticity of heteroporphyrins with computations
Paper

Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism

In this work we report a computational study about the aza-SNAr mechanism in fluorine- and chlorine-containing azines with the aim to unravel the physical factors that determine the reactivity patterns in these heterocycles towards propylamine.

Graphical abstract: Meisenheimer complexes as hidden intermediates in the aza-SNAr mechanism
Paper

Chemical transformations of push–pull fluorenones: push–pull dibenzodicyanofulvenes as well as fluorenone– and dibenzodicyanofulvene–tetracyanobutadiene conjugates

We report push–pull fluorenones (FOs) that can be transformed into dibenzodicyanofulvenes (DBDCFs). These FOs and DBDCFs, which contain a C[triple bond, length as m-dash]C bond, can subsequently be converted into tetracyanobutadiene conjugates.

Graphical abstract: Chemical transformations of push–pull fluorenones: push–pull dibenzodicyanofulvenes as well as fluorenone– and dibenzodicyanofulvene–tetracyanobutadiene conjugates
Open Access Paper

The intermolecular anthracene-transfer in a regiospecific antipodal C60 difunctionalization

The topochemically controlled regiospecific antipodal C60 difunctionalization proceeds via an ‘inverted sandwich’ with double-decker π–π-stacking interactions.

Graphical abstract: The intermolecular anthracene-transfer in a regiospecific antipodal C60 difunctionalization
Paper

Controlling the liberation rate of the in situ release of a chemical fuel for the operationally autonomous motions of molecular machines

Aminolysis of the anhydride of 2-cyano-2-phenylpropanoic acid can be employed to conveniently regulate the liberation rate of the related acid which, in turn, can be used as a fuel for acid–base operated molecular machines.

Graphical abstract: Controlling the liberation rate of the in situ release of a chemical fuel for the operationally autonomous motions of molecular machines
Paper

Origin of the ligand effect in the cobalt catalyzed regioselective hydroboration of 1,3-diene

The detailed mechanism and the origin of the ligand-controlled regioselectivity in the cobalt catalyzed hydroboration of 2-substituted 1,3-diene have been investigated.

Graphical abstract: Origin of the ligand effect in the cobalt catalyzed regioselective hydroboration of 1,3-diene
Paper

Enhanced reactivity of the pyrimidine peroxyl radical towards the C–H bond in duplex DNA – a theoretical study

The peroxyl radical exhibits a much stronger reactivity towards C1′–H1′ in duplex DNA with respect to single-stranded DNA.

Graphical abstract: Enhanced reactivity of the pyrimidine peroxyl radical towards the C–H bond in duplex DNA – a theoretical study
From the themed collection: Chemical biology in OBC
Paper

Chemo- and regioselective click reactions through nickel-catalyzed azide–alkyne cycloaddition

Nickel-catalyzed [3 + 2] cycloaddition reactions of unsymmetrical alkynes and organic azides afford substituted 1,2,3-triazoles with high levels of chemo- and regioselectivity.

Graphical abstract: Chemo- and regioselective click reactions through nickel-catalyzed azide–alkyne cycloaddition
From the themed collection: Synthetic methodology in OBC
Paper

The quasi-irreversible inactivation of cytochrome P450 enzymes by paroxetine: a computational approach

The potency of paroxetine as a P450 inhibitor is mainly attributed to the availability of two active sites on its structure, its compatibility with P450's active site and the ease of its tight coordination to heme iron.

Graphical abstract: The quasi-irreversible inactivation of cytochrome P450 enzymes by paroxetine: a computational approach
From the themed collection: Chemical biology in OBC
Paper

Proof of concept for poor inhibitor binding and efficient formation of covalent adducts of KRASG12C and ARS compounds

Comprehensive molecular modeling and kinetic analysis reveal a novel mechanism of the inhibition of the oncogenic mutant of the “undruggable” KRAS protein.

Graphical abstract: Proof of concept for poor inhibitor binding and efficient formation of covalent adducts of KRASG12C and ARS compounds
Paper

Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?

The localization of central NH protons in antipodally tetrasubstituted tetraphenylporphyrins suggested that suitable substitutions might also stabilize a porphyrin cis tautomer, a possibility that appears to be supported by DFT calculations.

Graphical abstract: Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?
Paper

Examination of pinanediol–boronic acid ester formation in aqueous media: relevance to the relative stability of trigonal and tetrahedral boronate esters

The “inverted” order of stabilities Ktrig > Ktet is observed for pinanediol boronate esters in spite of the existence of the usual strain release effect in the O–B–O angle of the cyclic diol ester.

Graphical abstract: Examination of pinanediol–boronic acid ester formation in aqueous media: relevance to the relative stability of trigonal and tetrahedral boronate esters
Paper

Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives

A DFT study is carried out in order to elucidate the racemization and cyclization mechanism as well as the atroposelectivity during the synthesis of 2-thiohydantoins. Computational data shows that the racemization occurs after cyclization with the assistance of triethyl amine.

Graphical abstract: Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives
Open Access Paper

Base-catalyzed C-alkylation of potassium enolates with styrenes via a metal–ene reaction: a mechanistic study

Base-catalyzed, C-Alkylation of potassium (K) Enolates with Syrenes (CAKES) enables practical synthesis or elaboration of pharmaceutical cores via a thusfar elusive mechanism. Herein, computational (DFT) and kinetic studies back a metal-ene reaction.

Graphical abstract: Base-catalyzed C-alkylation of potassium enolates with styrenes via a metal–ene reaction: a mechanistic study
From the themed collection: Catalysis & biocatalysis in OBC
Paper

Establishing linear-free-energy relationships for the quadricyclane-to-norbornadiene reaction

The kinetics of the thermal quadricyclane-to-norbornadiene (QC-to-NBD) isomerization follows a linear-free-energy relationship when using Creary radical Image ID:d0ob00147c-t1.gif values for a selection of aryl/cyano disubstituted derivatives.

Graphical abstract: Establishing linear-free-energy relationships for the quadricyclane-to-norbornadiene reaction
Paper

Amplification of the chiroptical response of UV-transparent amines and alcohols by N-phthalimide derivatization enabling absolute configuration determination through ECD computational analysis

Transformation of chiral UV-transparent amines and alcohols to phthalimides enhances their chiroptical response allowing their absolute configuration assignment by ECD computation.

Graphical abstract: Amplification of the chiroptical response of UV-transparent amines and alcohols by N-phthalimide derivatization enabling absolute configuration determination through ECD computational analysis
Paper

The pKa values of N-aryl imidazolinium salts, their higher homologues, and formamidinium salts in dimethyl sulfoxide

The effects of substitution, ring size and cyclisation on the pKa values of imidazolinium salts, higher homologues and formamidinium salts in DMSO are quantified, considering structural and electronic motifs along with crystallographic analyses.

Graphical abstract: The pKa values of N-aryl imidazolinium salts, their higher homologues, and formamidinium salts in dimethyl sulfoxide
Paper

How does cross-conjugation influence thiol additions to enones? A computational study of thiol trapping by the naturally occurring divinyl ketones zerumbone and α-santonin

DFT calculations show how the kinetics and thermodynamics of thiol additions to enones are affected by incorporation of the enone into a cross-conjugated divinyl ketone moiety.

Graphical abstract: How does cross-conjugation influence thiol additions to enones? A computational study of thiol trapping by the naturally occurring divinyl ketones zerumbone and α-santonin
Open Access Paper

Kinetic modelling of acyl glucuronide and glucoside reactivity and development of structure–property relationships

Detailed kinetic and transition structure modelling to rationalise the differences in reactivity observed between the acyl glucuronide and glucoside metabolites of a series of phenylacetic acid analogues.

Graphical abstract: Kinetic modelling of acyl glucuronide and glucoside reactivity and development of structure–property relationships
Paper

Mechanistic investigation into phenol oxidation by IBX elucidated by DFT calculations

Density functional theory (DFT) at the SMD/M06-2X/def2-TZVP//SMD/M06-2X/LANL2DZ(d),6-31G(d) level was used to explore the regioselective double oxidation of phenols by a hypervalent iodine(V) reagent (IBX) to give o-quinones.

Graphical abstract: Mechanistic investigation into phenol oxidation by IBX elucidated by DFT calculations
Paper

Looking at the big picture in activation strain model/energy decomposition analysis: the case of the orthopara regioselectivity rule in Diels–Alder reactions

The regioselectivity of the DA reaction is predicted by the ortho–para rule which has been explained from FMO theory. Using DFT calculations and ASM/EDA, we found that the results vary depending the position where it is performed.

Graphical abstract: Looking at the big picture in activation strain model/energy decomposition analysis: the case of the ortho–para regioselectivity rule in Diels–Alder reactions
Paper

The phosphorylation mechanism of mevalonate diphosphate decarboxylase: a QM/MM study

Combined MD and QM/MM studies suggested that mevalonate diphosphate decarboxylase requires two magnesium ions for a phosphorylation reaction.

Graphical abstract: The phosphorylation mechanism of mevalonate diphosphate decarboxylase: a QM/MM study
Paper

Mechanism and stereoselectivity of benzylic C–H hydroxylation by Ru–porphyrin: a computational study

Density functional theory calculations of an asymmetric benzylic C–H hydroxylation revealed the steric repulsion between the phenyl group of ethylbenzene and the bulky substituent of the D4-symmetric chiral Ru–porphyrin accounts for the stereoselectivity.

Graphical abstract: Mechanism and stereoselectivity of benzylic C–H hydroxylation by Ru–porphyrin: a computational study
Paper

The impact of cation structure upon the acidity of triazolium salts in dimethyl sulfoxide

The effect of structure on the pKa value of triazolium salts in dimethyl sulfoxide is quantified, considering common structural and electronic motifs. Included is the first pKa measurement of a triazolium salt that generates a mesionic carbene.

Graphical abstract: The impact of cation structure upon the acidity of triazolium salts in dimethyl sulfoxide
Paper

Electronic effects in tautomeric equilibria: the case of chiral imines from D-glucamine and 2-hydroxyacetophenones

Hammett plots show straightforward relationships for tautomeric equilibria in a new class of chiral imine–enamine structures.

Graphical abstract: Electronic effects in tautomeric equilibria: the case of chiral imines from d-glucamine and 2-hydroxyacetophenones
Paper

(3S,4R)-3,4-Dihydroxy-N-alkyl-L-homoprolines: synthesis and computational mechanistic studies

This is the first synthetic report of (3S,4R)-dihydroxy-N-alkyl-L-homoprolines described so far.

Graphical abstract: (3S,4R)-3,4-Dihydroxy-N-alkyl-l-homoprolines: synthesis and computational mechanistic studies
Paper

Systematic characterisation of the structure and radical scavenging potency of Pu'Er tea (Image ID:c9ob02007a-u1.gif) polyphenol theaflavin

Resolving the functional 3D structural poses of Pu'Er tea antioxidant theaflavin.

Graphical abstract: Systematic characterisation of the structure and radical scavenging potency of Pu'Er tea () polyphenol theaflavin
Paper

Gold(I)-catalyzed nucleophilic cyclization of β-monosubstituted o-(alkynyl)styrenes: a combined experimental and computational study

The diastereospecific 5-endo cyclization of β-monosubstituted o-(alkynyl)styrenes to 1-functionalized-1H-indenes is reported. The regiospecific generation of a cyclopropyl gold carbene intermediate is also supported by DFT calculations.

Graphical abstract: Gold(i)-catalyzed nucleophilic cyclization of β-monosubstituted o-(alkynyl)styrenes: a combined experimental and computational study
From the themed collection: Synthetic methodology in OBC
Paper

Theoretical insights into the E1cB/E2 mechanistic dichotomy of elimination reactions

Modeling the E1cB, E2, and E1cB/E2 borderline mechanisms in terms of carbanion stabilization.

Graphical abstract: Theoretical insights into the E1cB/E2 mechanistic dichotomy of elimination reactions
Paper

Mechanism of fatty acid decarboxylation catalyzed by a non-heme iron oxidase (UndA): a QM/MM study

QM/MM calculations reveal that the fatty acid decarboxylase UndA employs the FeIII–OO˙ complex to initiate the β-H abstraction with the monodentate coordination mode. The iron center accepts the extra electron of the substrate radical.

Graphical abstract: Mechanism of fatty acid decarboxylation catalyzed by a non-heme iron oxidase (UndA): a QM/MM study
Paper

An efficient synthesis of benzothiazole using tetrabromomethane as a halogen bond donor catalyst

A CBr4 catalyzed simple, mild, and efficient protocol has been developed for the synthesis of 2-substituted benzothiazole from 2-aminothiophenols and N-methylthioamides under solvent free conditions.

Graphical abstract: An efficient synthesis of benzothiazole using tetrabromomethane as a halogen bond donor catalyst
From the themed collection: Synthetic methodology in OBC
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The latest articles published in Organic and Biomolecular Chemistry related to mechanistic, computational & physical organic chemistry research.

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