Mikolaj Jawdosiuk

Highly strained single and double bonds

The infrared spectra of the strained single bond compounds, [2.2.lipropellane, {2.1.1]propellaneand [1.1.1]propellane, andthe vibrational and electronic spectra of the strained bridgehead double bond compounds, adamantene and azahomoadamantene, are reported and discussed.

Reduction potentials of anthelmintic drugs: Possible relationship to activity

Electrochemical data were acquired for several categories of anthelmintic agents, namely, iminium-type ions, metal derivatives and chelators, quinones and iminoquinones, and nitroheterocycles. Reductions usually were in the favorable range of +0.2 to -0.7 V versus normal hydrogen electrode. The drug effect is believed to result in part from either the catalytic production of oxidative stress or disruption of helminth electron transport systems. Relevant literature results are discussed.

A novel approach to β-lactam chemistry in vivo: Electron transfer and oxy radical formation by iminium

Abstract On binding to cell-wall enzyme, β-lactams form precursors of conjugated iminium species that apparently possess favorable reduction potentials based on studies with model compounds. The models used were iminium salts of Δ1-pyrroline-2-carboxylic acid and Δ3-thiazoline-4-carboxylic acid. Reduction potentials of −0.76 to −0.92 V increased to −0.18 to −0.37V with decrease in pH. The potentials of the iminium species are similar to those of well-known electron transfer (ET) agents, such as quinones, nitroheterocycles, and metal complexes. Catalytic ET by these cations is discussed in relation to nephrotoxicity, antibiotic action, and cell culture redox potential. Reactions of penicillin at the binding site are addressed. We propose that the bactericidal effect involves various modes of action, including inactivation of cell-wall enzyme and electrochemical interference with normal electron transfer processes.

Electron Transfer Mechanism for Cocaine Action

Although much progress has been made, there are many unanswered questions concerning the chemistry of the brain, including mechanistic features of central nervous system (CNS) drugs. It is reasonable to invoke the involvement of electrochemical phenomena in some cases, as was done in the pioneering investigations of Szent-Gyorgyi and co-workers1. The principal categories of electron transfer (ET) agents consist of quinones, metal complexes, ArNO2, and iminium ions2. In our prior work in the CNS area, iminium participation via ET was suggested for the action of benzodiazepines3, phencyclidine (PCP)4, nicotine4, mesoionics5, and 1-methyl- 4-phenyl-l,2,3,6-tetrahydropyridine (MPTP)6.

Photolysis and thermolysis of 3-azidonoradamantane. ‘Anti-bredt’ imines, 2-aza-adamant-1-ene, and 4-azaprotoadamant-3-ene

3-Azidoadamantane (1) when subjected to photolysis or thermolysis apparently forms the highly strained imines, 2-aza-adamant-1-ene (2), and 4-azaprotoadamant-3-ene (3). These reactive intermediates were trapped by ethanol or dibutylamine.

Synthesis of 3-Noradamantamine

Abstract Bridgehead primary amines in the bicyclic and tricyclic category have served as important intermediates in organic synthesis. When transformed into azo compounds, they can be used as a source of bridgehead free radicals.1 These amines also serve as precursors of azides which, when subjected to photolysis, lead to bridge-head imines (limits of Bredts rule).2 The N,N-dichloro derivatives undergo skeleton rearrangements in the presence of strong Lewis acids resulting in ring expansion with incorporation of nitrogen.3 Bicyclic and tricyclic bridgehead amines and their derivatives exhibit a wide spectrum of pharmacodynamical properties.4