A new stereoelectronic theory for the cleavage of the tetrahedral intermediate in the hydrolysis of esters and amides is presented. In this new theory, the precise conformation of the intermediate hemi-orthoester or hemi-orthoamide controls the nature of the hydrolysis products. It is postulated that the breakdown of a conformer of a tetrahedral intermediate depends upon the orientation of the ...

The preparation of a 1,3-bis(2,6-terphenyl)imidazol-2-ylidene, IDitop (Ditop=2,6-bis(4-tolyl)phenyl-) is reported. Several late transition metal complexes as well the selenium adduct were prepared to study and compare stereoelectronic properties other well-known N-heterocyclic carbenes (NHCs). A steric character taken from crystal structure data adducts reveals high degree flexibility. Prelimin...

AIDS is a pandemic responsible for more than 35 million deaths. The emergence of resistant mutations due to drug use is the biggest cause of treatment failure. Marine organisms are sources of different molecules, some of which offer promising HIV-1 reverse transcriptase (RT) inhibitory activity, such as the diterpenes dolabelladienotriol (THD, IC50 = 16.5 µM), (6R)-6-hydroxydichotoma-3,14-diene...

A stereoselective N-iminium ion cyclization with allylsilane to construct vicinal quaternary-tertiary carbon centers was developed for the concise synthesis of (±)-cephalotaxine. The current strategy features a TiCl4-promoted cyclization and ring-closure metathesis to furnish the spiro-ring system. The stereochemical outcome in the N-acyliminium ion cyclization was rationalized by the stereoele...

tant correlations between interproton coupling constants and structure available at the time. It cited 148 references, many of them multiple, and contained 109 structures with hundreds of numerical values for coupling constants as well as graphical and tabular results defining the variation of 1H~’Hcoupling constants with stereoelectronic factors. [The SCI® indicates that this paper has been ci...

tant correlations between interproton coupling constants and structure available at the time. It cited 148 references, many of them multiple, and contained 109 structures with hundreds of numerical values for coupling constants as well as graphical and tabular results defining the variation of 1H~’Hcoupling constants with stereoelectronic factors. [The SCI® indicates that this paper has been ci...

The structure of phenylcyclopropane radical cation (1•+, R ) H) is derived from CIDNP effects observed during the electron transfer reaction of 1 with chloranil. This species is an example of an elusive structure type. The secondary cyclopropane protons show significantly divergent hyperfine coupling constants due to an unprecedented stereoelectronic effect. Incorporation into a redox-active pe...

SYNTHESIS OF OLIGOSACCHARIDE MIMETICS BY THE DESULFURATIVEREARRANGEMENT OF ALLYLIC DISULFIDES AND STEREOELECTRONICINFLUENCE OF C-O BONDS ON CAND O-GLYCOSYLATIONbyMYRIAME MOUME-PYMBOCKMay 2013Advisor:Dr David CrichMajor:ChemistryDegree:Doctor of PhilosophyThis dissertation focuses on two different problems. The first part of thismanuscript ...