Discrimination among equals: A catalytic method for the selective oxidation of unprotected glycosides, both monosaccharides and disaccharides, has been developed. The resulting ketosaccharides are isolated in moderate to excellent yields. This approach provides a basis for protecting‐group‐free synthetic transformations of carbohydrates.

The reaction of readily available TEMPONa with aryl diazonium salts allows for clean generation of the corresponding aryl radicals along with TEMPO. Aryl radical addition to alkenes with subsequent TEMPO trapping provides the corresponding oxyarylation products in good to excellent yields. These experimentally easy to conduct transformations occur in the absence of any transition metal under mild conditions, and the process shows broad functional group compatibility.

A simple and practical method for the determination of rate constants for trifluoromethyl radical addition to various alkenes by applying competition kinetics is introduced. In the kinetic experiments the trifluoromethyl radicals are generated in situ from a commercially available hypervalent-iodine-CF3 reagent (Togni-reagent) by SET-reduction with TEMPONa in the presence of TEMPO and a π-acceptor. From the relative ratio of TEMPOCF3 and CF3-addition product formed, which is readily determined by (19)F-NMR spectroscopy, rate constants for trifluoromethyl radical addition to the π-acceptor can be calculated. The practical method is also applicable to measure rate constants for the addition of other perfluoroalkyl radicals to alkenes as documented for CF3CF2-radical addition reactions.

Reaction of various alkenes with commercially available N-fluorobenzenesulfonimide (NFSI) and TEMPONa provides the corresponding aminooxygenation products in moderate to good yields. Single electron transfer from readily generated TEMPONa to NFSI allows for clean generation of the corresponding bissulfonylamidyl radical along with TEMPO. N-radical addition to an alkene and subsequent TEMPO trapping provides the corresponding aminooxygenation product.

A simple and rapid method to determine gadolinium (Gd) concentrations in urine and blood plasma samples by means of total reflection X-ray fluorescence (TXRF) was developed. With a limit of detection (LOD) of 100 μg L(-1) in urine and 80 μg L(-1) in blood plasma and a limit of quantification (LOQ) of 330 μg L(-1) in urine and 270 μg L(-1) in blood plasma, it allows analyzing urine samples taken from magnetic resonance imaging (MRI) patients during a period of up to 20 hours after the administration of Gd-based MRI contrast agents by means of TXRF. By parallel determination of the urinary creatinine concentration, it was possible to monitor the excretion kinetics of Gd from the patient's body. The Gd concentration in blood plasma samples, taken immediately after an MRI examination, could be determined after rapid and easy sample preparation by centrifugation. All measurements were validated with inductively coupled plasma mass spectrometry (ICP-MS). TXRF is considered to be an attractive alternative for fast and simple Gd analysis in human body fluids during daily routine in clinical laboratories.

A novel method for selective generation of aryl radicals from diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPONa) as a single-electron transfer (SET) reducing reagent is described. In the presence of various alkenes, aryl radicals formed after SET-reduction of hypervalent iodine compounds undergo alkene addition and the adduct radicals that are thus generated are efficiently trapped by the concomitantly generated TEMPO radical to eventually afford oxyarylated products in moderate to very good yields. The efficiency of aryl radical generation of various iodine(III) reagents is studied and the generation of an iodanylidene malonate aryl radical is also investigated by computational methods.

Radical carboiodination of various aryl amines is reported. Aryl diazonium salts, generated in situ from the corresponding aryl amines, are reacted with Bu4NI to provide the corresponding aryl radicals which undergo 5-exo or 6-exo cyclization. Iodine abstraction eventually affords the carboiodinated products in good to excellent yields. If TEMPO is added, the cascade provides the cyclized carboaminoxylation products. Running the reaction in the presence of PhTeTePh affords the phenyltellurated cyclized products.

Einer unter Gleichen: Ungeschützte Glycoside, Mono‐ und Disaccharide, wurden mit der entwickelten katalytischen Methode selektiv oxidiert. Die erhaltenen Ketosaccharide wurden in mäßigen bis ausgezeichneten Ausbeuten isoliert. Dieser Ansatz bildet die Grundlage für schutzgruppenfreie synthetische Transformationen von Kohlenhydraten.