Stereoselective synthesis of novel beta,gamma-epoxyhydroxylamines and 4-hydroxyalkyl-1,2-oxazetidines

A simple and efficient stereoselective synthesis of polysubstituted beta,gamma-epoxyhydroxylamines and 4-hydroxyalkyl-1,2-oxazetidines, based on the addition of alpha-lithiated aryloxiranes to nitrones and subsequent cyclization of the corresponding intermediates in a 4-exo-tet mode, is described.     

Transfer of coenzyme Q0 from water to aqueous surfactant solutions: the case of Triton X-100

The effect of UQ0 on the micellization equilibrium of Triton X-100 has been studied by the analysis of the UV absorption spectra of Triton X-100. In the range of the UQ0 concentration investigated, the critical micelle concentration (CMC) increases at increasing of the solute concentration. The dependence of the CMC on UQ0 concentration has been used to calculate the generalized Setchenov constant. Mixing and dilution enthalpies of aqueous solutions of UQ0 and Triton X-100 were measured and used to calculate the enthalpies of transfer of UQ0 from water to Triton X-100 aqueous solutions. From the dependence of the enthalpy of transfer on surfactant concentration, the distribution constant between aqueous and micellar phase and the standard enthalpy of transfer from water to Triton X-100 micelles were evaluated along with the standard transfer free energy and entropy. All measurements were carried out at 298 K.     

Terminal oxazolinyloxiranes: synthesis, reaction with amines and regioselective β-lithiation

The synthesis of terminal oxazolinyloxiranes, even in enantioenriched form, has been performed by Darzens-type reaction of lithiated chloroalkyloxazolines with benzotriazolylmethanol (BtCH₂OH) or by chloromethylation of 2-acyl-2-oxazolines. The synthetic utility of such oxiranes based on their ability to act either as electrophiles, undergoing ring-opening reactions with nucleophiles, or as nucleophiles in form of the oxiranyl anions, generated by stereoselective β-deprotonation, has been investigated.     

A Zinc-Mediated Deprotective Annulation Approach to New Polycyclic Heterocycles

A straightforward approach to new polycyclic heterocycles, 1H-benzo[4,5]imidazo[1,2-c][1,3]oxazin-1-ones, is presented. It is based on the ZnCl₂-promoted deprotective 6-endo-dig heterocyclization of N-Boc-2-alkynylbenzimidazoles under mild conditions (CH₂Cl₂, 40 °C for 3 h). The zinc center plays a dual role, as it promotes Boc deprotection (with formation of the tert-butyl carbocation, which can be trapped by substrates bearing a nucleophilic group) and activates the triple bond toward intramolecular nucleophilic attack by the carbamate group. The structure of representative products has been confirmed by X-ray diffraction analysis.