The structures and energies of a variety of 10-X-2 ate-complexes derived from reaction of alkyllithiums and aryllithiums with the corresponding organohalides have been studied at the B3LYP/6-31+2G** theoretical level. The results of the calculations, which are in good agreement with the available experimental data, indicate that diaryl ate-complexes are more stable than their dialkyl counterpar...

Chiral 8-oxabicyclo[3.2.1]octane and 11-oxatricyclo[5.3.1.0]undecane are common structural motifs featured in many classes of natural products (Fig. 1), some of which show interesting biological activities. Englerin A, a potential anti-tumor reagent, is isolated from Phyllanthus engleri in Tanzania and shows selective activity to renal cancer cell lines at the nanomolar level. Balsamiferine J, ...

Ethanol is receiving great interest as an alternative fuel. Methanol is another alcohol fuel that could serve as a replacement for gasoline. Although it is currently receiving much less attention, it has the potential to play an important role. Like ethanol, methanol also has the advantage of being a liquid fuel and it can be produced from gasification of a variety of feedstocks using well esta...

Density functional theory computations at the B3LYP/6-31G(d,p) level have been carried out for three types of model compounds, viz. (i) 4-substituted bicyclo[2.2.2]octane carboxylic acids, (ii) anions of 4-substituted bicyclo[2.2.2]octane carboxylic acids and (iii) 4-substituted quinuclidines where the substituents are NO(2), CN, Cl, Br, CF(3), F, CHO, CH(2)Cl, COOH, COCH(3), CONH(2), OH, OCH(3...

α,β-Unsaturated N,N-dialkyl hydrazones undergo a mild [2 + 2] cycloaddition to allenamides when treated with a suitable gold catalyst. The method, which represents the first application of N,N-dialkyl hydrazones in gold catalysis, is compatible with a wide variety of substituents at the alkenyl moiety of the hydrazone component, proceeds with excellent levels of regio- and diastereoselectivity,...

The kinetics of the reactions between triphenylphosphine 1 and dialkyl acetylenedicarboxylates 2, in the presence of a NH-acid such as 5-nitroindazole 3,were studied. Corresponding kinetic parameters to all reactions were evaluated, with the second order rate constant (k) values calculated. Effects of solvent, temperature, and reactant...

The formation of striped phases of dialkyl disulfides on Au(111) and graphite has been monitored by scanning tunneling microscopy (STM). STM imaging clearly exhibits the formation of striped phases having corrugation periodicities that are nearly consistent with the molecular length of alkanethiolate moieties formed after the S-S bond cleavage of dialkyl disulfide on a gold surface. This is the...

Recent single-molecule experiments indicated that thioethers (dialkyl sulfides) on gold surfaces act as thermallyor mechanically activated molecular rotors, although the mechanisms for these phenomena are not yet clearly understood. Here we present theoretical and experimental investigations of the rotational dynamics of these thioether molecules. Single-molecule studies utilizing low-temperatu...