Source: Dissertation Abstracts International, Volume: 41-01, Section: B, page: 0204. / Thesis (Ph.D.)--The Florida State University, 1980.

A biomimetic synthesis of the lycorine-type Amaryllidaceae alkaloidslycorine (1), caranine (2) and pluviine (3) was attempted. Efforts to obtain a / high yield synthesis of hydroxyenone 4 from phenol 5 or 6 using external nucleophiles to trap the phenoxonium ion 7 or 8 were unsuccessful. / When amide 8 was oxidized with thallium (III) trifluoroacetate (TTFA)in trifluoroacetic acid (TFA), the amide oxygen efficiently trapped thephenoxonium ion 9 to yield oxazine 10 in good yield. All attempts to / convert 10 into 11 failed. Amide 12 was oxidized with TTFA in TFA,a mixture of dienone 13 and enone 14; however, when amide 12 wasoxidized with VOCl(,3) in anhydrous CH(,2)Cl(,2), only dienone 13 was obtained. The oxidation of amide 15 yielded only enoneester 16. The mechanism by / which 13, 14 and 16 were formed and the rationalization of the results were discussed. Attempted cyclization of enoneester 17, ketoester 18, hydroxyenone 19, hydroxyketones 20 and 21 to tetracyclic ketones 22-26, respectively, with lithium piperidide in ThF or by irradiation in DMSO/DMSO('-) were all unsuccessful. / Source: Dissertation Abstracts International, Volume: 42-01, Section: B, page: 0214. / Thesis (Ph.D.)--The Florida State University, 1981.

Source: Dissertation Abstracts International, Volume: 41-09, Section: B, page: 3446. / Thesis (Ph.D.)--The Florida State University, 1980.

A biomimetic synthesis of the taxane skeleton 4 (p. 5) was attempted. Lucas reagent catalyzed cationic cyclization of methyl geranylgeranate (20, p. 11) led to a mixture of compounds, none of which was isolated in pure enough form for definite indentification. Alternate synthetic approaches to the taxanes were investigated which involved the intermediacy of bicyclic enone 27 (p. 19); the latter was synthesized from dihydro-(beta)-ionone (26, p .19) in 26% yield by an initial Wittig reaction forming enamine 28 (p. 21) followed by condensation with ethyl vinyl ketone and cyclization to give 27 (p.19). Conversion of 27 to 4 required introduction of a one carbon unit. Hydrocyanation of 27 followed by allylic oxidation with CrO(,3)(.)2Pyr. and dehydrogenation with DDQ gave ketonitrile 49 (p. 29) as a mixture of all 4 isomers, in 24% yield from 27. Ketonitrile 49 was subjected to various reductive cyclization procedures which were unsuccessful. Dienone 37 (p. 24), nitroketone 38 (p. 24), p-nitrobenzoates 45 and 46 (p. 27), and ketoesters 75 and 76 (p. 37) were also subjected to anion forming conditions but did not cyclize. Stereochemical assignments of all compounds are discussed. / Source: Dissertation Abstracts International, Volume: 41-11, Section: B, page: 4117. / Thesis (Ph.D.)--The Florida State University, 1980.

A biomimetic synthesis of colchicine (1) was designed which required the intermediacy of enamine 2. The enamine was to be generated by decarboxylation or decarbonylation of the homomorphinandienone 3, formed by phenolic oxidative coupling of the phenethyltetrahydroisoquinoline 4. / (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) / Consequently Bischler-Napieralski cyclization of N- 3-(3,4,5-trimethoxyphenyl propanoyll-3-methoxy-4-hydroxyphenyl)alanine methyl ester was employed to give a 3,4-dihydrophenethyliso- quinoline, which was reduced with sodium borohydride to form a single diastereomeric tetrahydrophenethylisoquinoline. Acylation of the latter gave the N-trifluoroacetyl derivative, which when analyzed by X-ray diffraction, was shown to be the cis isomer. Epimerization of the amine followed by acylation gave the trans isomer, which was also analyzed by X-ray diffraction. / Intramolecular phenolic oxidative coupling of cis and trans-1-(3,4,5-trimethoxyphenethyl)-2-trifluoroacetyl-3-methoxycarbonyl-6-methoxy-7-hydroxy-tetrahydroisoquinolines was investigated. It was found that oxidative coupling of the trans derivative in dry toluene using iodosobenzene bistrifluoroacetate gave the best yield of homomorphinandienone (8%). Oxidation of the cis amide under the same conditions did not result in the formation of homomorphinandienone. / In view of the low yield obtained, an alternative pathway to 2 was investigated. O-Methylandrocymbine was synthesized in 34% yield by oxidation of the amine-borane of 1-(3,4,5-trimethoxyphenethyl)-2-methyl-6-methoxy-7-hydroxy-tetrahydroisoquinoline. Oxidation of O-Methylandrocymbine with hydrogen peroxide gave a diastereomeric mixture of N-oxides, which were each subjected to a modified Polonovski reaction using acetyl chloride. It was found that anti-elimination occurred to give the enamine 2. / Reaction of enamine 2 with both cyanogen azide and diphenylphosphoryl azide resulted in rearrangement to give the amidines 5 as the only identifiable products, in addition to two unidentifiable products. None of the desired colchicine derivative 6 could be found. / (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) / Source: Dissertation Abstracts International, Volume: 46-04, Section: B, page: 1174. / Thesis (Ph.D.)--The Florida State University, 1984.

Part one describes a systematic study of the Michael addition of enolates to $\alpha,\beta$-unsaturated esters and thioesters. Numerous examples of high stereoselectivity have been discovered, and the factors that influence the stereoselection were examined. The use of the potassium enolate in the sequential Michael addition has been explored. Two consecutive Michael additions can be achieved with excellent diastereoselectivity. These results are consistent with a chelated transition state. Furthermore, asymmetric Michael additions of thioamide and ester enolates to chiral crotonates have been undertaken. Optically pure diastereomers were isolated by fractional recrystallization and the configuration of the Michael adducts were solved by single crystal X-ray crystallography and chemical correlations. / Part two describes a systematic study of the stereochemistry of the Michael addition of ester enolates to 3-alkoxy-2-bromoacrylates. The effects of the ether and ester alkyl substituents in the Michael acceptor and donor on the stereochemical outcome were investigated. These results are consistent with a chelated transition state. Asymmetric Michael additions utilizing chiral propionate ester enolates and methyl 2-bromo-3-methoxyacrylate have been carried out. A number of high asymmetric inductions were observed, and the factors controlling the facial selectivity were discussed. Optically pure Michael adducts were isolated and provided precursors for synthetic studies leading to Lonomycin A. / Source: Dissertation Abstracts International, Volume: 57-04, Section: B, page: 2574. / Major Professor: Robert A. Holton. / Thesis (Ph.D.)--The Florida State University, 1996.

Picosecond absorption spectroscopy permitted direct detection of several new reactive intermediates in bond dissociation reactions. / Our study of 9-fluorenol and related substituted fluorenes led to a spectral assignment for the 9-fluorenyl cation, HFl$\sp+$, which exhibits a $\lambda\sb{\rm max}$ at 515 nm and has a lifetime of $<$20 ps in 9:1 H$\sb2$O/CH$\sb3$OH. In the non-nucleophilic solvent, trifluoroethanol, this lifetime increases to 1.25 ns. The 9-methyl-9-fluorenyl cation, which absorbs at 485 nm and has a lifetime of 275 ps in 9:1 H$\sb2$O/CH$\sb3$OH, was also characterized. The absorption spectrum of the 9-fluorenol cation radical was assigned to a 640-nm band which previously was assigned incorrectly to HFl$\sp+$. / Picosecond-pulsed irradiation of 9-diazofluorene in hexanes, cyclohexane, CH$\sb2$Cl$\sb2$, and CH$\sb3$CN permitted the observation of a precursor of the ground-state triplet carbene, 9-fluorenylidene ($\sp3$Fl:). The precursor absorbs at 415 nm in CH$\sb3$CN and is quenched by added CH$\sb3$OH with an apparent second-order rate constant of (2.3 $\pm$ 0.4) $\times$ 10$\sp9$ M$\sp{-1}$ s$\sp{-1}$. The 415-nm absorption band is assigned to singlet fluorenylidene, $\sp1$Fl:. This is the first observation of a singlet carbene which is not the ground state in room-temperature solution. / The photochemistry of diaryliodonium salts was found to be highly dependent on the identity of the counterion: diphenyliodonium salts with complex counterions such as BF$\sb4\sp-$ or PF$\sb6\sp-$ decompose in CH$\sb3$CN or CH$\sb2$Cl$\sb2$ via the iodobenzene cation radical to produce iodobenzene and protic acid. Salts with halide counterions, on the other hand, behave quite differently: excitation of diphenyliodonium chloride (Ph$\sb2$I$\sp+$ Cl$\sp-$), causes electron transfer to occur from Cl$\sp-$ to the diaryliodonium cation, which is followed by loss of a phenyl radical to form an iodobenzene/chlorine-atom complex ($\lambda\sb{\rm max}$ = 460 nm). The same complex is formed upon irradiation of iodobenzene dichloride. / The unsymmetrical p-anisylphenyliodonium salts exhibit similar behavior; however, the iodoanisole/chlorine-atom complex is unstable, and undergoes back-electron transfer to give the iodoanisole cation radical and chloride with a rate k = 6.7 $\times$ 10$\sp{10}$ s$\sp{-1}$. / Source: Dissertation Abstracts International, Volume: 51-09, Section: B, page: 4348. / Major Professor: Edwin F. Hilinski. / Thesis (Ph.D.)--The Florida State University, 1990.

Substituted benzoyl peroxides in which one of the moieties is p-methoxybenzoyl (anisoyl) and the other has one or more nitro substituents are known to decompose heterolytically as well as homolytically. In polar media the decomposition reactions are faster than those in non-polar media and the free radical derived products begin to be accompanied by ion pair derived products such as the carboxy inversion compound. The surface of silica favors the polar reaction more than do ordinary polar solvents. / The literature contains evidence that bis(p-methoxybenzoyl) peroxide (AP) may also react in part by a polar mechanism, even in relatively nonpolar solvents. The rate for the peroxide with a single p-methoxy substituent in dioxane also exceeds that predicted by the Hammett plot. The thermolysis of AP at room temperature in silica gel slurries made with nonpolar solvents is several orders of magnitude faster than the corresponding reaction in solution. The rate is dependent on the choice of solvent, the type of silica gel, and the loading of the silica gel surface. The major initial product of the decomposition is the carboxy inversion product, anisoyl anisyl carbonate (APCI). The reaction was followed by conventional methods, as well as solid state $\sp{13}$C NMR spectroscopy. / The products from the decomposition of benzoyl peroxide (BP) in ordinary solvents (excluding those due to reaction with the solvent) are the acid, ester and carbon dioxide. The thermolysis of BP on silica gel in the absence of solvent at 40$\sp\circ$ was about 22 times as fast as the rate calculated for a dilute benzene solution at that temperature and gave products derived almost entirely from ionic precursors. Thermolysis on silica gel at 80$\sp\circ$ was only about 3 times as fast as the reaction in benzene and gave products derived largely from radical and only to a lesser extent from ionic precursors. Photolysis at 25$\sp\circ$ gave only radical-derived products. / Source: Dissertation Abstracts International, Volume: 50-08, Section: B, page: 3475. / Major Professor: John E. Leffler. / Thesis (Ph.D.)--The Florida State University, 1989.

The acid-catalyzed cyclizations of various aromatic diazoacetamides were studied and general and efficient preparations of isoquinolinones, benzazepinones, and spirodienone lactams were realized. The scope and limitations of these cyclization reactions were investigated. / In the presence of anhydrous trifluoroacetic acid, $\alpha$-unsubstituted $N$-methyldiazoacetamides were cyclized to give isoquinolinones in 60-80% yield. Cyclization of the diazoacetamides under these conditions, except with immediate addition of water, afforded spirodienone lactams in similar yields. Formation of the spirocycles under the rapid aqueous quench conditions demonstrated the intermediacy of spirodienone oxonium ions formed via preferential exo-trig cyclization. The cyclizations of other $\alpha$-unsubstituted $N$-methyldiazoacetamides were found to proceed similarly to afford isoquinolinones, benzazepinones, and spirodienone lactams. A limitation to this method was encountered when $\alpha$-substituted $N$-methyldiazoacetamides were found to cyclize to spirodienone lactams in only 10-20% yield. The inefficient cyclization of $\alpha$-substituted diazoacetamides was attributed to a conformational effect. To overcome this effect, $\alpha$-substituted $N$-tert-butyldiazoacetamides were prepared and were efficiently cyclized to 1-substituted isoquinolinones in 60-80% yield. / Spirodienone lactams prepared by this method were demonstrated to be synthetically useful. Rearrangement of these compounds in the presence of boron trifluoride etherate in refluxing nitromethane proceeded regiospecifically to afford phenolic isoquinolinones in 80-90% yield. / The described reactions were employed in synthetic approaches to the alkaloids morphine and colchicine. / Source: Dissertation Abstracts International, Volume: 50-03, Section: B, page: 0969. / Major Professor: Martin A. Schwartz. / Thesis (Ph.D.)--The Florida State University, 1989.

Source: Dissertation Abstracts International, Volume: 40-07, Section: B, page: 3179. / Thesis (Ph.D.)--The Florida State University, 1979.