Ein direkter C-C-Kupplungsprozess, bei dem Michael-Akzeptoren und Eschenmosersalz zusammengeführt werden, wird vorgestellt. Obwohl er an die Morita-Baylis-Hillman-Reaktion erinnert, benötigt dieser Prozess keinen Lewis-Base-Katalysator. Der zugrundeliegende Mechanismus konnte durch eine Kombination aus kinetischen Isotopenmarkierungsexperimenten computergestützten Untersuchungen aufgeklärt krit...

The recently established NOAA Hurricane Forecast Improvement Project (HFIP) has set a 5-year goal to reduce track and intensity forecast errors by 20%, and a 10-year goal for a 50% reduction. The 10-year goal corresponds to an average error reduction of 5% per year. Figure 1 shows the annual average 48 h Atlantic track and intensity errors of the National Hurricane Center (NHC) official forecas...

Herein, we report the first examples of the synthesis of pyrroloindolines by means of (3 + 2) dearomative annulation reactions between 3-substituted indoles and highly reactive azaoxyallyl cations. Computational studies using density functional theory (DFT) (B3LYP-D3/6-311G**++) support a stepwise reaction pathway in which initial C-C bond formation takes place at C3 of indole, followed by ring...

In this manuscript, we report clear evidence for the generation of aromatic cation radicals produced by using [hydroxy(tosyloxy)iodo]benzene (HTIB) in fluoroalcohol solvents such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The single-electron-transfer (SET) oxidation ability of HTIB to give cation radicals was first established by ESR and UV measurements. The r...

An antibacterial cyclic AS-48 protein was chemically synthesized by a-ketoacid–hydroxylamine (KAHA) ligation. Initial challenges associated with the exceptionally hydrophobic segments arising from the amphiphilic nature of the protein were resolved by the development of bespoke reaction conditions for hydrophobic segments, using hexafluoroisopropanol (HFIP) as a co-solvent. The synthetic protei...

An antibacterial cyclic AS-48 protein was chemically synthesized by α-ketoacid-hydroxylamine (KAHA) ligation. Initial challenges associated with the exceptionally hydrophobic segments arising from the amphiphilic nature of the protein were resolved by the development of bespoke reaction conditions for hydrophobic segments, using hexafluoroisopropanol (HFIP) as a co-solvent. The synthetic protei...

Pseudo-benzylic substitution is an important reaction in the ferrocene series, especially to obtain ligands for catalysis. Herein, we described new reactions conditions, using fluorinated alcohols as both solvent and promoter, able deliver iodoferrocene derivatives faster than classical solvents. Various N, O, P C-nucleophiles were found compatible with this transformation which occurs full ret...

A tandem 1,3-sulfur migration followed by iodocyclization reaction of propargylic sulfides in the presence NIS HFIP has been developed to synthesize indene-based β-iodoalkenyl sulfides. The choice media is crucial promote reaction. proposed mechanism involving initial activation and favoring sulfur starting thioether via cationic intermediates experimentally supported. In addition, suitability ...