Synthesis of oxychelerythrine using lithiated toluamide-benzonitrile cycloaddition

Oxychelerythrine, benzo[c]phenanthridine alkaloid, was synthesized from easily available starting toluamide 5 and benzonitrile 6 using toluamide-benzonitrile cycloaddition reaction in 6 steps.     

Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography

A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods.     

Graph bisection algorithms with good average case behavior

In the paper, we describe a polynomial time algorithm that, for every input graph, either outputs the minimum bisection of the graph or halts without output. More importantly, we show that the algorithm chooses the former course with high probability for many natural classes of graphs. In particular, for every fixedd≧3, all sufficiently largen and allb=o(n ^{1?1/[(d+1)/2]}), the algorithm finds the minimum bisection for almost alld-regular labelled simple graphs with 2n nodes and bisection widthb. For example, the algorithm succeeds for almost all 5-regular graphs with 2n nodes and bisection widtho(n ^2/3). The algorithm differs from other graph bisection heuristics (as well as from many heuristics for other NP-complete problems) in several respects. Most notably:

1. the algorithm provides exactly the minimum bisection for almost all input graphs with the specified form, instead of only an approximation of the minimum bisection,
2. whenever the algorithm produces a bisection, it is guaranteed to be optimal (i.e., the algorithm also produces a proof that the bisection it outputs is an optimal bisection),
3. the algorithm works well both theoretically and experimentally,
4. the algorithm employs global methods such as network flow instead of local operations such as 2-changes, and
5. the algorithm works well for graphs with small bisections (as opposed to graphs with large bisections, for which arbitrary bisections are nearly optimal).

     

1,4-Addition of benzene to a dihydrocyclopent[a]indene diradical: synthesis and DFT study

Photochemical cyclization of compound 1, a homoenediyne (-CCC=CCH2CC-) bearing two ethynylanthracene chromophores, yields two isomeric dihydrocyclopent[a]indene ring systems, spiro-fused to the 9-position of a 9,10-dihydroanthracene moiety. Evidence of a photochemically initiated diradical cyclization pathway is proposed on the basis of (i) hydrogen abstraction from reaction with 1,4-cyclohexadiene (1,4-CHD) and (ii) the observation of 1,4-addition of benzene (solvent). The reaction was further analyzed by a complete density functional theory (DFT) study, using an unrestricted approach (UBLYP) with a 6-31G* basis set for the open-shell triplet states of the reactants, products, and diradical intermediates to model the photochemical nature of observed transformation. A mechanism detailing the observed cyclization/addition reaction is proposed.     

Catalytic phenomena in the electrochemical reduction of triphenylphosphine and triphenylphosphine oxide in non-aqueous solvents with tetraalkylammonium supporting electrolytes

Polarography, cyclic voltammetry and coulometry reveal that a catalytic reduction of the tetraalkylammonium cation, R₄N⁺, of the supporting electrolyte is involved in the electrochemical reduction of triphenylphosphine (TPP) and its oxide (TPPO) in aprotic solvents such as acetonitrile, dimethylformamide and hexamethylphosphoramide. There is however progressive consumption of TPP and TPPO resulting in the final formation of phenyl substitution products (RPØ₂ and ROPØ₂). Comparison with the reduction of the BuPØ₃⁺ cation allows to propose the following mechanism which involves a chemical type catalytic process:

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Redox type catalytic mechanisms are discussed and shown to be unlikely. Values of the alkylation rate constant are derived from the polarographic or the coulometric data or from cyclic voltammetry according to its magnitude which varies with the solvent. TPP anion radical appears as more readily alkylable than TPPO anion radical.     

Neosappanone A, a xanthine oxidase (XO) inhibitory dimeric methanodibenzoxocinone with a new carbon skeleton from Caesalpinia sappan

A novel dimeric methanodibenzoxocinone, named neosappanone A (1), possessing a unique unprecedented novel carbon framework, has been isolated from the heartwood of Caesalpinia sappan L. of Vietnam, and its structure was elucidated on the basis of spectroscopic analysis. Neosappanone A (1) competitively inhibited xanthine oxidase in a concentration-dependent manner (IC₅₀, 29.7 μM; K_i, 16.3 μM).     

Kinetics of the hydrogen abstraction *CH3 + alkane --> CH4 + alkyl reaction class: an application of the reaction class transition state theory

Kinetics of the hydrogen abstraction reaction (*)CH(3) + CH(4) --> CH(4) + (*)CH(3) is studied by a direct dynamics method. Thermal rate constants in the temperature range of 300-2500 K are evaluated by the canonical variational transition state theory (CVT) incorporating corrections from tunneling using the multidimensional semiclassical small-curvature tunneling (SCT) method and from the hindered rotations. These results are used in conjunction with the Reaction Class Transition State Theory/Linear Energy Relationship (RC-TST/LER) to predict thermal rate constants of any reaction in the hydrogen abstraction class of (*)CH(3) + alkanes. Our analyses indicate that less than 40% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER method while comparing to explicit rate calculations the differences are less than 100% or a factor of 2 on the average.     

Synthesis of novel tryptamine and β-carboline derivatives via palladium-catalyzed reaction of bromotryptamine with organic boronic acids

New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids. Dedicated to Professor András Lipták on his 70^th birthday.     

Domino "[3+3]-cyclization-homo-Michael" reactions of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes

The Lewis acid mediated domino "[3+3]-cyclization-homo-Michael" reaction of 1,3-bissilyl enol ethers with 1,1-diacylcyclopropanes allows an efficient one-pot synthesis of functionalized salicylates containing a halogenated side chain. A great variety of substitution patterns could be realized by variation of the starting materials and of the Lewis acid. The mechanism of the domino process was studied.     

Selective reduction of aldehydes by a formic acid- trialkylamine- RuCl2(PPh3)3 system

In the presence of trialkylamine and formic acid RuCl₂(PPh₃)₃ selectively reduces aldehydes to the corresponding alcohols at room temperature. Other reducible groups are unaffected.