Chapter I describes the synthesis of a trishomocubyl helical tubuland diol and some aspects of its inclusion chemistry. Thus, all three isomers of 4,7-dimethylpentacyclo[6.3.0.0^2,6.0^3,10.0^5,9]undecane-4,7-diol have been prepared and their X-ray structures have been determined. The syn,syn-isomer crystallizes in a double-stranded hydrogen-bonded lattice, while anti,syn-isomer forms a hydrogen-bonded layer lattice. In contrast, the anti,anti-isomer is a new member of the helical tubuland diol host family; its crystal lattice consists of parallel canals with a trefoil-shaped cross-section of area 25.4 Å^2. Chapter II describes the synthesis of new molecular clefts. These molecular clefts have been synthesized via base-promoted reactions of 3,6-diaryl-l,2,4,5-tetrazines with tetracyclo[6.3.0.0^4,11.0^5,9]undecane-3,6-dione and with tricyclo[6.3.0.0^2,6]undecane-3,11-dione, respectively. Compounds of this type are of interest as a potential new class of host molecules for use in host-guest complexation studies. Chapter III reports the synthesis of stereospecifically deuterated spiro(oxetane-3,8'-pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecanes) and their acid-promoted ring opening and concomitant rearrangements. The deuterium-containing reaction products have been characterized via analysis of their NMR and mass spectra. The results strongly suggest that intramolecular 1,5-hydride shifts provide an important pathway through which the acid promoted rearrangements occur. Chapter IV reports the oxidation of heptacyclo-[6.6.0.0^2,6.0^3,13.0^4,11.0^5,9.0^10,14] tetradecane (HCTD) via application of Barton's "GoAgg" systems. The products have been characterized by NMR and mass spectral analysis. Under GoAgg^v conditions, oxidation of HCTD proceeds to afford heptacyclo [6.6.0.0^2,6.0^3,13.0^4,11.0^5,9.0^10,14]tetradecan-7-one in 1% yield.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc278447 |
| Date | 12 1900 |
| Creators | Wang, Yanjun |
| Contributors | Marchand, Alan P., Norton, S. J., Bott, Simon G., Acree, William E. (William Eugene), Jones, Paul R. |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | xiii, 240 leaves : ill., Text |
| Rights | Public, Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved., Wang, Yanjun |
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