A new intersection between reaction chemistry and electronic circuitry is emerging from the ultraminiaturization of electronic devices. Over decades chemists have developed a nuanced understanding of stereoelectronics to establish how the electronic properties of molecules relate to their conformation; the recent advent of single-molecule break-junction techniques provides the means to alter th...

Using molecular mechanics (MM2, MM3) and semiempirical molecular orbital methods (EHMO, AMI, PM3) the relative energies were estimated from models for the tetrahedral intermediates in N->0 and o~N acyl migration in diastereoisomers of 3-amino-1,2,3triphenylpropanol to check the necessity of invoking a stereoe!ectronic effect to explain their reactivities . The molecular mechanics results correc...

The effect of N-aglycones at C1’ on the drive of two-state north (N (C3’-endo-C2’-exo)) * south ( S (C2’endo-C3’-exo)) pseudorotational equilibrium in 8-D-ribofuranosyl-N-nucleosides consists of two counteracting contributions from (i) the anomeric effect (stereoelectronic interactions between furanose 04’ and the nucleobase nitrogen at Cl’), which places the aglycone in the pseudoaxial orienta...

Fluorine substituents have become a widespread and important drug component, their introduction facilitated by the development of safe and selective fluorinating agents. Organofluorine affects nearly all physical and adsorption, distribution, metabolism, and excretion properties of a lead compound. Its inductive effects are relatively well understood, enhancing bioavailability, for example, by ...

BACKGROUND There is a dearth of treatment options for community-acquired and nosocomial Pseudomonas infections due to several rapidly emerging multidrug resistant phenotypes, which show resistance even to combination therapy. As an alternative, developing selective promiscuous hybrid compounds for simultaneous modulation of multiple targets is highly appreciated because it is difficult for the ...

Anomeric O-alkylation/arylation is applied to the synthesis of 2-deoxy-beta-glycosides. Treatment of lactols with NaH in dioxane followed by the addition of electrophiles leads to the formation of 2-deoxy-beta-glycosides in high yield and high selectivity. The high beta-selectivity observed here demonstrates a powerful stereoelectronic effect for the stereoselective formation of acetals under k...

An efficient, regioselective gold-catalyzed 1,3-transposition reaction of ynones and diynones has been developed. It was found that stereoelectronic (interrupted conjugation) and electronic (extended conjugation) factors could efficiently govern the regioselectivity of this thermodynamically controlled transformation. The produced conjugated diynones were efficiently transformed into diverse al...

The synthesis of a model endocyclic allene related to the vernonia allenes is described. Fragmentation of a suitable decalin derivative gave the simplified germacrane scaffold. Computational analysis of this and related substrates provides insight into the stereoelectronic requirements of C-C fragmentation. The overall strategy to access these and other sesquiterpenes and the key steps in the p...