Part I, Fluorination of organostannanes with xenon difluoride and silver triflate ; Part II, Approach to (-)-11-Nor-[delta]⁹-THC-carboxylic acid and synthesis of cannabinoid analogs

Kawakami, Joel Kenji
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Part I: Fluorination Of Organostannanes With Xenon Difluoride And Silver Triflate. The first successful transformation of vinyl stannanes to vinyl fluorides has been accomplished using xenon difluoride and silver(I). The reaction occurs regio- and stereospecifically. The use of silver triflate has been found to be optimal for the fluorination reaction. Although related work has appeared in the literature since our initial publication, our method still offers the fastest rate of reaction and yields for our process are competitive. The mechanism has been extensively investigated. Although our findings are not definitive, we have been able to conclusively eliminate certain mechanistic pathways. Radical mechanisms, which are common for xenon difluoride, are not occurring during our fluorination. Various functional groups in the vinyl stannane are tolerated in the fluorination. The fluorination is rapid, with typical reaction times of 5 min or less. Due to the short half-life of 18F (approx. 110 min), a short reaction time is required for in vivo metabolic studies of 18p labeled compounds using PETT. Therefore, our fluorination reaction may offer a versatile 18F labeling method. Part II: Approach To (-)-Nor-Δ9-Tetrahydrocannabinol (THC)-9-Carboxylic Acid And Synthesis Of Cannabinoid Analogs. The concern over marijuana abuse has led to the development of a bioassay for detecting marijuana metabolites. The major human urinary metabolite of marijuana is ll-nor-Δ9-THC-9-carboxylic acid which arises from the oxidation of Δ9-THC, a major constituent of marijuana. As a consequence, the need for this metabolite as a standard for the bioassay has led to several synthetic studies. Notwithstanding, there is still the need for an improved synthetic route for ll-nor-Δ9-THC-9-carboxylic acid. This part of the dissertation will address all of the strategies for improving the previous work. Due to Δ9-THC's antiemetic effect, its use for patients receiving cancer chemotherapy has been legalized in U.S.A. However, the concern over its prolonged use has led to a search for cannabinoid analogs which exhibit antiemetic and not euphoric effects. Reported in this part of the dissertation are the synthesis of cannabinoid analogs which will be bioassayed by Professor A. M. Makriyannis and coworkers at the University of Connecticut.
On t.p. "[delta]" appears as the Greek symbol.
Thesis (Ph. D.)--University of Hawaii at Manoa, 1994.
Includes bibliographical references (leaves 257-262).
xiv, 262 leaves, bound ill. 29 cm
Fluorination, Tetrahydrocannabinol, Cannabinoids -- Synthesis
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Theses for the degree of Doctor of Philosophy (University of Hawaii at Manoa). Chemistry; no. 3097
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