Keywords: Charge transfer / NMR spectroscopy / Density functional calculations / Rhodium / IridiumOur recent results of the chemistry of group 9 Rh and Ir metal complexes bearing the ubiquitous pyridine, diimine (PDI) terdentate nitrogen donor are reviewed. Examples reflecting the special nature of the PDI ligand include a facile C-H activation process and the stabilization of a very rare late transition metal iridium nitrido compound, (PDI)IrϵN, and its direct hydrogenation to the corresponding amido complex according to (PDI)IrϵN + H 2 Ǟ (PDI)Ir-NH 2 . The amount of electron transfer to the PDI ligands in (PDI)Rh,Ir-R,X com-

The 3-decalinoyltetramic acid (-)-hymenosetin and its N-methyl analogue were prepared in 11 and 8 steps, respectively, from (+)-citronellal using an intramolecular Diels-Alder reaction as the key step. This method represents the first example for the synthesis of a 3-decalinoyltetramic acid with a free NH moiety. The stereochemistry of the title compound, an unnatural diastereomer, and of a decalin building block was studied in detail using circular dichroism spectroscopy in the IR and UV/VIS freqeuncy range. This allowed to determine the absolute configuration of the natural product and to plan the synthetic route.

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The absolute configurations of a series of phytotoxic dioxolanone‐type secondary metabolites isolated from culture filtrates of the grape black rot fungus Guignardia bidwellii were determined by vibrational circular dichroism (VCD) spectroscopy in the mid‐IR frequency range. Comparison of the recorded data with DFT calculations showed good agreement between experiment and theory for VCD, whereas electronic circular dichroism (ECD) data for the compounds matched poorly with the predicted spectra obtained by time‐dependent DFT (TDDFT) calculations at the same level of theory.

The iodocyclization of o-alkynylbenzamides with various electrophiles has been reported to yield five- or six-membered lactams by nucleophilic attack of the amide nitrogen onto the triple bond. While the formation of an isobenzofuran-1(3H)-imine with two bulky substituents under Larock conditions was initially attributed to steric hindrance, we found out that cyclization via the amide oxygen is the rule rather than the exception. Thus, the structures of the products reported in the literature need to be revised.