<p> This thesis describes the development of the Wittig olefination reaction of stabilized, semistabilized allylic trialkylphosphorus ylides with various aldehydes to afford E olefins mainly (E>89%). Since the steric demand of trialkylphosphorus ylides was decreased, aldehydes achieved high E selectivity. On the other hand, predominant or exclusive formation of Z olefms was achieved by using allylic triphenylphosphorus ylides and aromatic aldehydes like benzylaldehyde, while the combination of allylic triphenylphosphorus ylides and such sterically hindered aldehydes as cyclohexanecarboxaldehyde led to E olefm formation upon ylide formation with LiHMDS. In the case of olefination reactions of aldehydes with dimethyl thiazole ylide, it was shown that among the aromatic aldehydes only 4-nitrobenzaldehyde reacted with this ylide and provided a pure E olefin product (41% yield). Dimethylmalonyltributylphosphorane (DMTP) reacted with aromatic aldehydes in toluene at 125 °C to give the corresponding alkenes. 4-Nitrobenzaldehyde· gave the alkene in a much higher yield (81%), followed by 4-chlorobenzaldehyde (31%). With benzaldehyde, the corresponding olefin was isolated in only 14% yield under these conditions. Clearly, this highly stabilized ylide only enters into reaction with electron deficient aldehydes. A possible approach to Z-a, P-unsaturated aldehydes was investigated through the olefination of an acetal-ylide followed by hydrolysis. However, E acetal olefins were in fact isolated from this 2'-(1,3-dioxolanyl)-triethylphosphorus ylide with aromatic aldehydes in good yields (62%-76%). This result is still mechanistically interesting in view of the chemoselective formation of such an ylide in the presence ofthree ethyl substituents on phosphorus. </p> <p> Class of flavonoids: Sakuranetin, Naringenin and (28)-7-methoxy-6hydroxyflavanone, have been isolated from the diseased bark of Prunus sp. The structures were elucidated based on the spectroscopic data. Locations of 4-keto, 5-0H and 7-methoxy were deduced from COSY and HMBC spectra. Such compounds are of interest for their potential antibiotic activity against vancomycin-resistant strains of microbes. </p> / Thesis / Master of Science (MSc)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/21435 |
| Date | 04 1900 |
| Creators | Huang, Ying |
| Contributors | McNulty, James, Chemistry |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
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