post-Spin Crossing Dynamics Determine the Regioselectivity in Open-shell Singlet Biradical Recombination

Radical recombination is among the fastest reactions in organic chemistry. Achieving high level of selectivities in this type of reactions is rather challenging. In a recent report on visible-light-induced dearomative...

PolyDODT: A Macrocyclic Elastomer with Unusual Properties

The effect of reaction conditions on the structure of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H2O2 and air was investigated. 800 MHz (1 and...

Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts

Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C–S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C–S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C–S cleavage and radical recombination step.

The ozonolysis of cyclic monoterpenes: a computational review

Monoterpenes are prevalent organic compounds emitted to the atmosphere, via biogenic activities in various types of plants. Monoterpenes undergo atmospheric decomposition reactions derived by the potent atmospheric oxidizing agents, OH, O3, and NOx. This review critically surveys literature pertinent to the atmospheric removal of monoterpenes by ozone. In general, the ozonolysis reactions of monoterpenes occur through the so-called Criegee mechanism. These classes of reactions generate a wide array of chemical organic and inorganic low vapor pressure (LVP) species. Carbonyl oxides, commonly known as Criegee intermediates (CIs), are the main intermediates from the gas-phase ozonolysis reaction. Herein, we present mechanistic pathways, reactions rate constants, product profiles, thermodynamic, and kinetic results dictating the ozonolysis reactions of selected monoterpenes (namely carene, camphene, limonene, α-pinene, β-pinene, and sabinene). Furthermore, the unimolecular (vinyl hydroperoxide and ester channels) and bimolecular reactions (cycloaddition, insertion, and radical recombination) of the resulting CIs are fully discussed. The orientations and conformations of the resulting primary ozonides (POZs) and CIs of monoterpenes are classified to reveal their plausible effects on reported thermokinetic parameters.