ERASSTRI - European Risk Assessment Study on Synthetic Turf Rubber Infill - Part 2: Migration and monitoring studies.

End-of-life tyre (ELT)-derived rubber granules are used as synthetic turf infill on sports fields. They contain various chemical substances and there are concerns that exposure to these substances might be harmful for human health. In this second part of a Europe-wide study to address these concerns migration of substances from rubber granules to artificial body fluids (sweat, saliva, gastric juice) was tested and exposure measurements at sports fields were performed to improve the database for exposure assessment. Some PAHs, aluminium, cobalt, benzothiazole, tert-butylamine, MIBK, 4-tert-octylphenol, bisphenol A, and the phthalates DINP and DEHP were found in at least some samples of sweat simulant. The migration rates calculated with these data were used to inform the dermal exposure assessment. In artificial saliva and gastric juice, only aluminium, cobalt, 4-tert-octylphenol and MIBK were detected and migrated fractions were calculated. Bioaccessibility from rubber granules in the gastrointestinal tract was estimated conservatively, assuming complete availability for most substances. In addition, air samples from 17 sports fields in six European countries were analysed. There were no increased concentrations of metals (aluminium, cobalt), PAHs, or other semivolatile substances in air samples, but some volatiles (MIBK: 95th percentile: 18 µg/m3, benzothiazole: 95th perc.: 7 µg/m3, tert-butylamine: 95th perc.: 31 µg/m3, 2-heptanone: 95th perc.: 0.4 µg/m3, cyclohexanone: 95th perc.: 1.5 µg/m3, and saturated aliphatic hydrocarbons >C9: 95th perc.: 26 µg/m3) were slightly increased in a few samples. In addition, skin wipe samples were obtained from 43 sportspeople after playing on synthetic turfs. Only aluminium was detected above the limit of quantification in these samples (95th perc.: 0.84 mg/sample). These data are important input for risk characterisation as performed in the final study phase. Bioaccessibility data are used for estimating oral and dermal exposure of sportspeople, and air measurements are essential for inhalation exposure assessment.

Asymmetric Synthesis of Spirobenzazepinones with Atroposelectivity and Spiro-1,2-Diazepinones by NHC-Catalyzed [3+4] Annulation Reactions.

A strategy for the NHC-catalyzed asymmetric synthesis of spirobenzazepinones, spiro-1,2-diazepinones, and spiro-1,2-oxazepinones has been developed via [3+4]-cycloaddition reactions of isatin-derived enals (3C component) with in-situ-generated aza-o-quinone methides, azoalkenes, and nitrosoalkenes (4atom components). The [3+4] annulation strategy leads to the seven-membered target spiro heterocycles bearing an oxindole moiety in high yields and excellent enantioselectivities with a wide variety of substrates. Notably, the benzazepinone synthesis is atroposelective and an all-carbon spiro stereocenter is generated.

Asymmetric, Three-Component, One-Pot Synthesis of Spiropyrazolones and 2,5-Chromenediones from Aldol Condensation/NHC-Catalyzed Annulation Reactions.

A novel one-pot, three-component diastereo- and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,ß-unsaturated pyrazolones, which react with a second equivalent of enal through an N-heterocyclic carbene (NHC)-catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3-diketones, 2,5-chromenediones are available through [2+4] annulation.

Catalytic Conia-ene and related reactions.

Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

Asymmetric synthesis of fully substituted cyclopentane-oxindoles through an organocatalytic triple Michael domino reaction.

An efficient, highly stereoselective asymmetric synthesis of fully functionalized cyclopentanes bearing an oxindole moiety and several other functional groups in one pot has been developed. Key step is an organocatalytic triple Michael domino reaction forming three C-C bonds and six stereocenters, including a quaternary one. Starting from equimolar amounts of simple substrates, a high molecular complexity can be reached after a Wittig olefination in one pot. The new protocol can easily be scaled up to gram amounts.

An Asymmetric Organocatalytic Quadruple Domino Reaction Employing a Vinylogous Friedel-Crafts/Michael/Michael/Aldol Condensation Sequence.

An organocatalytic quadruple cascade initiated by a Friedel-Crafts-type reaction is described. The (S)-diphenylprolinol trimethylsilyl ether catalyzed reaction yields highly functionalized cyclohexenecarbaldehydes bearing a 1,1-bis[4-(dialkylamino)phenyl]ethene moiety and three contiguous stereogenic centers. The reaction tolerates various functional groups and all products are obtained with very good diastereoselectivity and with virtually complete enantiomeric excess.