This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
The yields from the oxidation of 4-methylpyrimidine with potassium permanganate were found to increase from 25 to 92 percent by the addition of small amount of potassium hydroxide to the reaction mixture. Pyrimidine-4-carboxylic acid decarboxylates in hot aqueous solution to yield pyrimidine and carbon dioxide. The rate is that decarboxylation...
Studies toward the total syntheses of highly potent cytotoxic alkaloids
including the bromopyrrole alkaloids and indole alkaloids were conducted and are
described. Studies carried out in the course of this dissertation consist of five total syntheses of natural products that include bromopyrrole alkaloids nagelamide A, D and agelastatin D as...
Ultraviolet spectroscopic methods for the determination
of dissociation constants can only be applied to
those compounds having protonatable sites conjugated with
or inherent in a chromophoric group of the compound.
The determination of the dissociation constants of
organic nitrogeneous bases by ultraviolet spectroscopic
methods was found to be only reliable...
The objectives of this study were to isolate 2, 4-diaminobutyric
acid and to attempt cyclizing the acid and its disulfonamide derivative.
The original synthetic method by Adamson was followed but a
modified isolation procedure for the acid was employed.
Following the synthesis, the acidic solution was passed through
Dowex-3 ion-exchange...
Enantioenriched sp³-hybridized carbenoid reagents CR1R2MX (X = nucleofuge, M = electrofuge) of different types were investigated for the synthesis of polysubstituted alkyl chains by iterative stereospecific reagent-controlled homologation (StReCH) and for the stereospecific connective synthesis of alkenes by eliminative cross-coupling.
In the first part, putative enantioenriched α-chloroalkyllithiums (CHRLiCl) were employed...
Sulfoxide-ligand exchange (SLE) and asymmetric halogen-metal exchange (AHME) processes were separately examined for the enantioselective synthesis of functionalized alpha-haloalkylmetal (carbenoid) reagents. Carbenoids derived from SLE were used to effect stereospecific reagent-controlled homologation (StReCH) of boronic esters and those generated via AHME were engaged in Darzens-type chemistry with aldehydes.
Abstract for...
Iodine-129 is a key risk driver at sites where nuclear materials have been fabricated or processed, and it is a predominant isotope of concern in long-term waste storage strategies. I-129 exists primarily as iodate in the subsurface at the Hanford Site in south-central Washington State. Between 15 and 40% of...
PART I. The preparation of (-)-ibogamine (1) in fourteen steps from benzoquinone and in 10% overall yield is a powerful illustration of the value of the asymmetric Diels-Alder reaction as a starting point in a multistep synthesis. All four cycloadducts, 70, 77, 84 and 96, obtained with the (S)-BINOL-TiCl₂ complex...