RESUMO
Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.
RESUMO
Alkanes in the presence of berberine sulfate provide an enhancement of fluorescent signal, which depends on alkane concentration and structure, when the system is irradiated with monochromatic UV light. Computational analysis suggests that an ion-induced dipole between alkanes and berberine sulfate is responsible for this phenomenon. This interaction can properly model the experimentally obtained fluorescent response. The proposed explanation allows other interacting systems to be designed, which have been experimentally confirmed.
RESUMO
Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.
RESUMO
The regioselectivity of the cycloaddition of N-methylazomethine ylide to C70 can be modified by using microwave irradiation as the source of energy. Under microwave irradiation and by choosing the appropriate solvent and irradiation power, the 5-6 isomer is the major product, a situation that is in contrast to conventional heating where the 1-2 isomer predominates. Moreover, isomer 7-21, which represents 13% of monoadducts under classical heating, is not formed under microwave irradiation and with ODCB as solvent. Theoretical calculations predict an asynchronous mechanism and suggest that the modification of the regiochemical outcome is related to the relative energies and hardnesses of the transition structures involved.
RESUMO
Fluorescence enhancement of a broad variety of solutes has been used extensively in TLC although no thorough explanation has been proposed. In this work, we try to understand it and explore new applications to which it can be put. In this way, alkanes can be quantitatively determined by fluorescence scanning densitometry using silica gel plates impregnated with berberine sulfate. Molecular simulation and analysis of molecular orbitals allows this phenomenon to be explained in this case and lays the groundwork to explain fluorescence enhancements produced by other molecules. A ion-molecule interaction between alkanes and berberine sulfate is responsible for the enhancement of fluorescence produced by alkanes. Computational results suggest that the surrounding alkane molecules provide an apolar environment to the berberine cation, thus enhancing the intensity of the fluorescence signal. This proposed explanation has been tested by extending the fluorescence determination to other compounds. These include biologically interesting saturated and unsaturated fatty acids, steroids and derivatives, prostaglandins, ceramides, galactocerebrosides, as well as terpenes, and polypropylene glycols. In addition, according to the proposed explanation, the properties required for alternative impregnants to berberine are discussed.
