Three new glucosylceramides (GluCers) named malusides I–III (1–3) were isolated from apple (cultivars of Malus domestica) pomace (fruit material remaining after juice extraction). An unusual oxo/hydroxy group pattern within the sphingadienine (d18:2) type sphingoid base was observed. All compounds contained the same α-hydroxylated fatty acid (h16:0) and a β-D-glucose moiety. Their structures were assigned on the basis of one- and two-dimensional (1D and 2D) nuclear magnetic resonance (NMR) spectroscopic analyses and mass spectrometry (MS) measurements.

The first total synthesis of cordyheptapeptide A is described. The synthesis is accomplished by a convergent approach featuring a combination of peptide coupling and the Ugi reaction for the preparation of the main building blocks and the acyclic precursor. The assembly of an N-methylated fragment by the Ugi reaction comprised the utilization of a convertible isonitrile followed by activation of the C-terminal amide. Two different macrocyclization sites were evaluated, proving greater efficacy the macrolactamization at the site Ile-Tyr, likely due of a more suitable conformational bias of the acyclic precursor having an internal β-turn centered at the N-Me-d-Phe-Pro moiety.

Organocatalytic nucleophilic addition of 2-hydroxylnaphthaquinone to imines is reported. This new route can be used to produce enantioenriched Mannich bases with excellent yields and moderate enantioselectivities.

Three new pyridine alkaloids were detected in the pygidial glands of some Stenus species. The chemotaxonomic significance of the occurrence of these alkaloids and stenusine in different Stenus species is discussed. The antimicrobial properties of (Z)- and (E)-3-(2- methyl-1-butenyl)-pyridine and the deterrent activities of stenusine and norstenusine were investigated.

The complex pigment pattern of fly agaric (Amanita muscaria) cap skins has been studied by LC-DAD and mass spectrometry. Among the betaxanthins the corresponding derivatives of serine, threonine, ethanolamine, alanine, Dopa, phenylalanine and tryptophan are reported for the first time to contribute to the pigment pattern of fly agarics. Betalamic acid, the chromophoric precursor of betaxanthins and betacyanins, muscaflavin and seco-dopas were also detected. Furthermore, the red-purple muscapurpurin and the red muscarubrin were tentatively assigned while further six betacyanin-like components could not be structurally allocated. Stability studies indicated a high susceptibility of pigment extracts to degradation which led to rapid colour loss thus rendering a complete characterization of betacyaninlike compounds impossible at present. Taking into account these difficulties the presented results may be a starting point for a comprehensive characterization of the pigment composition of fly agarics.

The scope of chromium(II)-mediated Takai-Utimoto ­reactions was extended to previously unconvertable secondary alkylhalides. Optimization allowed yields of up to over 95%.

Small libraries of peptoid-based macro(multi)cycles were produced by applying combinatorial principles to the MiB methodology. This combinatorial approach features the incorporation of varied building blocks into the resulting macrocycles by mixing all the components in the same reaction pot. Both skeletal and appendage diversity could be generated in one shot due to the multicomponent nature of the system. HPLC and ESI-MS analyses showed a well-distributed composition of the libraries and revealed the presence of all possible macrocycles resulting from the different combinations of building blocks, especially of members with differentially substituted bridges not available by any other one-pot ­approach.

The application of 2-(2,2-dimethoxyethyl) phenyl iso­nitrile in Ugi, Passerini, and Ugi-Smiles reactions is described. The simple transformation to highly activated indolyl amides allows functional-group conversion of the isonitrile moiety into a variety of carboxylic acid derivatives, overall acting as a neutral, nucleophilic COOH equivalent.

N-Tritylaziridino alcohols have been easily synthesized in a straightforward synthetic route from an inexpensive and easily available chiral pool. They were used in the enantioselective alkenylzinc additions to aldehydes furnishing the products in excellent yields and stereoselectivities up to 97%.

For the first time, homo-Mannich reactions with unmasked homoenolates have been achieved by adding homoenolate precursor 1 and imines 5. The key to this reaction is the right choice of the Lewis acids - Cu(OTf)2 proved to be most suitable for preparing the homoenolate and activation of the imine. An asymmetric catalytic version of this reaction is provided by using chiral, non-­racemic phenyl-derived bisoxazolidine as ligand for the Lewis acid.