Optically active 1,3-dioxolan-2-yl cation intermediates were generated during enantioselective dioxyacetylation of alkene with chiral hypervalent iodine(III). Regioselective attack of a nucleophile toward the intermediate resulted in reversal of enantioselectivity of the dioxyacetylation.

Tris(perfluoroalkyl)phosphines, of interest as tunable alternatives to the carbon monoxide ligand, can be synthesised by the nucleophile mediated reaction of perfluoroalkyltrimethylsilanes with triphenylphosphite; the method can be extended to diphosphines.

2-Dimethylalkylammonium pyridinium and 2-dimethylalkylammonium pyrimidinium ditriflate salts are very powerful methylating agents toward phosphorus (triphenylphosphine) and nitrogen (triethylamine) nucleophiles. In competition experiments with triethylamine as nucleophile, these N-methyl disalts are more reactive methylating agents than dimethyl sulfate. Reaction of the pyridinium dications wit...

1. The self-catalysed hydrolyses of the thiol esters, S-hippurylthioglycollic acid and S-ethyl monothiolsuccinate, have been shown to be slower than the deacylation step for the papain-catalysed hydrolysis of hippuric esters, by a factor approx. 10(5). This difference in rate constants largely reflects a difference in activation energy, which together with other evidence drawn from the literatu...

Hypervalent iodine(III)-mediated dioxygenation and diamination of alkenes have been previously developed. In this study, the potential application of hypervalent iodine(III) reagent was successfully extended to the dialkylation and cyclopropa(e)nation of unsaturated alkenes and alkynes. The reactions of alkenes with malononitrile and other active methylene compounds as the carbon nucleophiles g...

Nucleotidyl-transfer reaction catalyzed by DNA polymerase is a fundamental enzymatic reaction for DNA synthesis. Until now, a number of structural and kinetic studies on DNA polymerases have proposed a two-metalion mechanism of the nucleotidyl-transfer reaction. However, the actual reaction process has never been visualized. Recently, we have followed the nucleotidyl-transfer reaction process b...