Table of Contents

Abstract: The results presented in this paper confirm that the stereochemical outcome of the reversible additions of lithium (R)-methyl p-tolyl sulfoxide to N-arylidene-p-anisidines (NPMP imines) depends on: (a) the reaction conditions used and (b) the electronic properties of the arylidene moiety on the starting imine. In particular, we show that under kinetic control (-70 °C) the additions involving electron-rich N-arylidene groups occur with very high stereocontrol in favor of the (2S,RS)-diastereomers, whereas an electron-deficient group favors the opposite stereochemical outcome. Based on the observations above, a mechanistic hypothesis is proposed.

Abstract: Berberine azide, berberine thiocyanate, and 8-cyano-8H-berberine were prepared from berberine chloride, a quaternary protoberberine alkaloid. The molecular and crystal structures of all compounds are reported and discussed.

Abstract: A facile and efficient synthetic procedure for effecting the pinacol rearrangement catalyzed by AlCl₃ in the absence of solvent is developed. The rearrangement product is obtained at room temperature in a few minutes and in almost quantitative yield. Benzylic pinacols rearrange under these conditions, while aliphatic pinacols do not react.

Abstract: Neuropeptide Y (NPY), a 36-mer neuromodulator, binds to the receptors Y₁, Y₂, Y₄ and Y₅ with nanomolar affinity. They all belong to the rhodopsin-like G-protein coupled, seven transmembrane helix spanning receptors. In this study, Ala-substituted and centrally truncated NPY analogues were compared with respect to affinity to the Yreceptors. Furthermore, antibodies against the second (E2) and the third (E3) extracellular loop of NPY Y₁-, Y₂- and Y₅-receptor subtypes were raised and affinity to intact cells was tested by immunofluorescence assays. Both methods were applied in order to receive subtype selective tools and to characterise ligand binding. The analogues [A¹³]-pNPY and [A²⁷]-pNPY showed subtype selectivity for the Y₂-receptor. Sera against the E2 loop of the Y₁-receptor and against the E2 loop of the Y₂-receptor were subtype selective. Two antibodies against the Y₅ E2 and E3 loop recognised the Y₅- and Y₂-receptor subtypes. In combination, these sera are able to distinguish between the Y₁-, Y₂-, and Y₅-receptor subtypes. The analogues and antibodies represent valuable tools to distinguish NPY receptors on membranes and intact cells.

Abstract: The epoxidation of the natural product α-euphol followed by cleavage of the obtained epoxide with BF₃-etherate, provides 3β-hydroxy-eupholanost-8-en-24-one in satisfactory overall yield.

Abstract: o-Quinodimethane can be generated from =α,α'-dihalo-o-xylenes using zinc in aqueous solution. In the presence of activated dienophiles cycloadducts can be obtained directly. Catalysis with tris-triphenylphosphine ruthenium(II) dichloride reduces side reactions such as reduction and polymerisation and improves the yield. This is the first example of an organometallic cyclisation in aqueous medium using dihalo compounds.

Abstract: The synthesis of 2,4,6-tris(4-N-isopropylamidinophenyl)pyrimidine from 1,3-di(4-bromophenyl)propen-3-one and 4-bromobenzamidine is reported.

Abstract: A series of neat 4-(2-alkenyl) substituted 5-methyl-3-phenyl-4H-1,2,4-triazoles were thermolyzed at 320 ^oC producing a rearrangement products, of which the regioisomeric 1- and 2-substituted triazoles were the main products. The group migrations were rationalized in terms of consecutive S_N2-type reactions. This mechanism was supported by a study of the alkylations of the triazoles which gave similar product mixtures. 4-(2-alkenyl) substituted 3-phenyl-4H-1,2,4-triazoles, on the other hand, gave predominantly elimination products.