This study consists of four major areas of research. First, the relationship between and was extended to Lrl nil homoallylic couplings and was used to determine the relative degree of puckering in a series of dihydroaromatic carboxylic acids. Second, the effect of coupling contributions transmitted through space were examined by theoretical calculations of the intermediate neglect of differential overlap finite perturbation theory type (INDO-FPT) including selective overlap reduction experiments to determine the sign and magnitude of the major through-space contributions and the effect of the orientation of the substituent upon the vicinal carbon3 carbon coupling. Third, the dependence of the J upon substituent orientation in norbornanes was empirically investigated by the synthesis of a series of lactones and cyclic ethers whose conformation was rigid and known. Fourth, a large number of norbornanes substituted with methyls in the 1, 3, and 7 position and a carbon-13 labeled substituent in the 2 position were synthesized and studied in order to obtain a variety of vicinal C-C couplings; all the NMR parameters for this series of compounds were determined while the carbon13 labeled substituent was varied from methyl to methylene to carbinol to aldehyde and to carboxylic acid.

The body of information concerning carbon-carbon spin-spin coupling constants now includes a large number of coupling constants, the establishment of a dihedral angular dependence on 3JCC, and the application of 3JCC to conformational analysis. This study adds another dimension to the growing wealth of information associated with 13 C-NMR: the influence of some non-bonded interactions on 3JCC Four types of non-bonded interactions that could influence vicinal carbon-carbon NMR coupling constants were investigated. To facilitate the NMR studies, a variety of 13C-labeled compounds were synthesized.

The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.