| dc.description.abstract | The stereochemistry and mechanism of the iron pentacarbonyl-induced coupling of strained olefins (e.g., 7-phenylnorbornadiene) to carbon monoxide is discussed. Emphasis is placed on determination of the structure of one dimeric ketone coupling product with the aid of the lanthanide shift reagent Eu(fod)(, 3) in nuclear magnetic reso- nance decoupling experiments. Also demonstrated is the use of a computer program which calculates the equilibrium constants (K(, 1) and K(, 2)) and bound chemical shifts ((DELTA)1 and (DELTA)2) for the one step (L + S (DBLHARR) LS) and the two step (LS + S (DBLHARR) LS(, 2)) lanthanide shift reagent-dimeric ketone interactions (L(, m)S(, n)). The position of the europium atom in the L(, 1)S(, 1) "collision-complex" is determined with the aid of another computer program. New iron carbonyl coupling products and unique cage compounds synthesized from them are discussed. Introduction of easily replaceable thallium ditrifluoroacetate into biologically active compounds and its eventual substitution by radioactive iodine (for use as an imaging agent in tracer studies) is investigated. Finally, the synthesis of a series of several interesting and highly strained polycyclic pentacyclo 5.4.0.0('2,6).0('3,10).0('5,9) - undecane-8,11-diones is demonstrated, comprehensive ('1)H and ('13)C NMR signal assignments are made using high resolution con- ventional and 2-dimensional nuclear magnetic resonance tech- niques, and the X-ray crystal structure of the 3-methylpentacyclo- 5.4.0.0('2,6).0('3,10).0('5,9) undecane-8,11-dione isomer is demonstrated. | en_US |
