Frank Alber,†,‡,§ Gerd Folkers,‡ and Paolo Carloni*,†,§,| International School for AdVanced Studies SISSA/ISAS, Via Beirut 4 I-34014 Trieste, Italy, Department of Pharmaceutical Chemistry, Swiss Federal Institute of Technology (ETH), CH-8057 Zürich, Switzerland, INFM-Istituto Nazionale per la Fisica della Materia, Italy, International Centre for Genetic Engineering and Biotechnology, AREA Scien...

Protein motion is intimately linked to enzymatic catalysis, yet the stereoelectronic changes that accompany different conformational states of a substrate are poorly defined. Here we investigate the relationship between conformation and stereoelectronic effects of a scissile amide bond. Structural studies have revealed that the C-terminal glycine of ubiquitin and ubiquitin-like proteins adopts ...

Abstract In polymer mechanochemistry, mechanosensitive molecules (mechanophores) are activated upon elongation of anchored arms. The reactivity a mechanophore can be influenced by variety structural factors, including the geometry attachment arms and nature eventual substituents. Here we investigate stereoelectronic effects in force-accelerated Diels–Alder reactions using CoGEF (Constrained Geo...

In three 9-silyltriptycenes bearing chlorine, bromine and the methyl group in one of the peri positions, the silyl group suffers extreme hindrance of its reorientational motion. Owing to this, separate signals of the individual silyl group protons could be observed in NMR spectra at relatively high temperatures. For each compound, the measured values of J couplings of these protons to the 29Si ...

An efficient synthesis of the C4-epi-lomaiviticin B core is reported. The synthesis features a diastereoselective anionic formal furan Diels-Alder reaction and a stereoselective oxidative enolate dimerization. During the investigation, subtle yet critical stereoelectronic effects imparted by the C4-stereocenter were observed.

Two isomeric pairs of cisand trans-1-cyclohexyl-2-phenyl-3-benzoylaziridines have been synthesized: (1) with a nitrogen-15 labelled nitrogen, and (2) with carbon-13 labelled ring carbons. The carbon-13 to X (where X=nitrogen-15, carbon-13 or hydrogen-I) spin-spin coupling constants were measured and interpreted in terms of stereoelectronic effects. X-ray crystallographic data (earlier determine...