A new synthetic approach to the key intermediate in the stereoselective synthesis of (2S,3R)-capreomycidine was developed. The synthesis is based on novel domino reaction combining (3,3)-sigmatropic rearrangement of chiral allylic thiocyanate derived from D-methionine and intramolecular amino addition to arising isothiocyanate to produce diastereommerically (4R,5R)-4-vinyltetrahydro-1H-imidazole-2-thione.

Four easy eco-friendly laboratory procedures are presented for the oxidative iodination of various arenes with molecular iodine, in the presence of sodium percarbonate as the oxidant. The purified mono- or diiodinated products were obtained in 60-92% yields.

Benzene, halobenzenes, and a number of more or less deactivated arenes, including nitrobenzene, readily reacted in anhydrous HIO3/AcOH/Ac2O/concd H2SO4 mixtures to probably give ArIO2 intermediates or other hypervalent species (not isolated). The final reaction mixtures were poured into excess aq. Na2SO3 solution (a reductor) to give the purified iodinated products in 39-83% yields.

A number of more or less deactivated arenes, ArH, were effectively mono- or diiodinated with strongly electrophilic I+ reagents prepared from either diiodine or potassium iodide and with added sodium periodate, and reacted for 30 min at 25 – 30 °C in concd (min. 95%) sulfuric acid. The iodinating I+ solutions thus obtained were always applied in a 10% excess in respect to the reacted arenes, with using either the “direct” method or the “inverse” method of aromatic iodination explained in the text. The yields for the iodinated pure products varied from 17% to 91%.

The new method of arylalkylketones Clemmensen reduction to alkylbenzenes with zinc dust and hydrochloric acid was elaborated. A comparison of arylalkylketones Clemmensen reduction with zinc amalgam literature method was made. The direction of reaction is the same, the yield of alkylbenzenes is often slightly higher. The conditions of reaction are the same or slightly milder than classic conditions.

Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns were obtained from meso-4-[(3-N,N-dimethylaminopropoxy)phenyl]dipyrromethane 1, which was formed by the condensation of 4-(3-N,N-dimethylaminopropoxy)benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59 %. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid (TFA) under different conditions. First, 1 was reacts with 4-(3-N,N-dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (~4 times TFA/1 molar ratio) to obtain 6.2 % of 5,10,15,20-tetrakis(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A4-porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3-N,N-dimethylaminopropoxy]phenyl)-10,20-di(4-trifluoromethylphenyl)porphyrin (A2B2-porphyrin) with 4.8 % yield. Also, this procedure yields a mixture of porphyrins, which were formed due to acidolysis of 1. When minor amount of TFA was used in acetonitrile the yield of A2B2-porphyrin was very poor (~0.4 %). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3-N,N-dimethylaminopropoxy)benzaldehyde catalyzed by TFA (~2 times TFA/1 molar ratio) in acetonitrile yields 9.3 % of 5-(4-trifluoromethylphenyl)-10,15,20-tris(4-[3-N,N-dimethylaminopropoxy]phenyl) porphyrin (A3B-porphyrin). Also, A2B2 and A4 porphyrins were isolated with 6.0 and 2.0 %, respectively. Finally, exhaustive methylation of amino porphyrins produce cationic sensitizers (>94 % yields). In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge, which also provides a higher mobility of the charge facilitating the interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacteria inactivation by photodynamic therapy.

Tetraphenylantimony(V) carboxylates, triphenylantimony, triphenylbismuth have been used in the Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxides such as (PhCO2)2, t-BuOOH, H2O2 under mild conditions (20-50 °?). The peroxides promote a cascade participation of organoantimony compound to provide transfer of two or three phenyl groups with the formation of methylcinnamate as a sole product. Organobismuth compound gives methylcinnamate, biphenyl and benzene simultaneously.