Themed collection Mechanistic Aspects of Organic Synthesis

There is no consensus of opinion on the origin of the large rate accelerations observed for enzyme-catalyzed hydride transfer.

The strained heterocyclic alkyne, 3-oxacyclohexyne, has been generated for the first time by a photochemical route.

4-(Furan-2-ylamino)but-2-en-1-yl acetates are converted to substituted indoles under microwave heating in the presence of catalytic tetrakis(triphenylphosphine)palladium(0) and triisopropylphosphite.

Divergencies unravelled in new Pt-catalysed alkoxy- and hydroxycyclisation of N-tethered 1,5-bisallenes to give vinyl-tetrahydropyridines with alcohols and hydro-1H-azepines with water.

Unraveling the factors affecting the regioselectivity in the ring-expansions of bicyclic aziridiniums.

A DFT study of the enantioselective organocatalytic intramolecular Morita–Baylis–Hillman (IMBH) reaction of enones under the influence of 1,1,1,3,3,3-hexafluoroisopropanol is reported. This study establishes an excellent fit between the experiment and theory.

Bis-adducts of cyclohexa-1,4-diene with dihalocarbenes were synthesized and investigated in heterocyclization.

The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed.

Epoxide hydrolase (EH) enzymes catalyze the hydration of racemic epoxides to yield their corresponding vicinal diols. In this work, the Bacillus megaterium epoxide hydrolase (BmEH)-mediated hydrolysis of racemic styrene oxide (rac-SO) and its para-nitro styrene oxide (rac-p-NSO) derivative are computationally investigated using density functional theory (DFT).

A designed N,N′-dialkyldiketopiperazine (DKP) provides evidence for the role of DKP additives as initiators that act by electron transfer in base-induced homolytic aromatic substitution reactions, involving coupling of haloarenes to arenes.

DFT and DFT/MM calculations are applied to a photocatalytic enantioselective reaction and shown to be able to characterize the mechanism.

Thorough computational studies were performed on mechanisms and energies for the thermal trimerizations of neutral or electron-rich acetylenes used as cross-linkers in organic hard-masks for lithography applications.

DFT reveals why arenes with an amide or anilide directing group react faster by C–Si than by C–H cleavage in Pd coupling reactions.

Computational investigations reveal that pnicogen bonding, a noncovalent interaction between the electrophilic region of a phosphorus atom and a Lewis base, can activate electrophiles in catalytic reactions.

Theoretical calculations are reported which examine the mechanisms of Claisen rearrangements of benzyl vinyl ethers and the ways in which substituents influence reactivity and regioselectivity.

Intradiol vs. extradiol selectivity of Fe(III)-complexes explained by spin-state consistent density functionals.

A new mass-spectrometry method allows monitoring the key role of the gold–gold interaction in the transformation of gold salts to bases.

Experimental and computational evidence for unusual intramolecular hydrogen-bonding interactions is presented and discussed.

Irradiation of nanocrystals of azide 1 results in a solid-to-solid photoreaction that forms imine 2 in high chemical yield.

This work provides a comprehensive model for non-enzymatic phosphoryl transfer, as a baseline for understanding biological phosphoryl transfer reactions.

Insights into [1,j] sigmatropic proton shifts in polyenyl anions and related conjugated systems have been revealed by quantum chemical calculations.

A palladium-catalyzed oxidation reaction is disclosed where the nitrile functionality on the substrate simply changes the course of the reaction. α-Cinnamyl β-keto nitriles provide α,β,γ,δ-diene containing β-keto nitriles with good substrate scope.

gem-Dimethyl substitution at C3 enhances the preference for β-lactone formation from 2-chlorosuccinate but methylation at C2 almost favours α-lactone.

Computation elucidates the mechanism and origins of regioselectivity of (NHC)Ni(II)hydride-catalyzed cycloisomerization of dienes.

DFT calculations were performed to study systematically the influence of borole substituents on the reaction of boroles with carbon monoxide.

Herein a bis(pyridyl)-N-alkylamine/Cu^I/TEMPO/NMI catalyst system is reported for aerobic oxidation of a variety of primary alcohols to the corresponding aldehydes using readily available reagents, at room temperature and ambient air as the oxidant.

The nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene and ethanol was examined in a series of ionic liquids across a range of mole fractions.

A detailed computational study is presented on the reaction mechanism of ynamide-mediated condensation of carboxylic acids with amines to produce amides, which elucidates the reactivity pattern of the coupling reagent ynamide and discloses crucial bifunctional catalytic effects of the carboxylic acid substrate during aminolysis.