The submarine Amsterdam-St. Paul (ASP) Plateau, bisected by the Southeast Indian Ridge (SEIR), is a bathymetric high rising ~2 km above the surrounding seafloor that includes the islands of Amsterdam and St. Paul; this excess volcanism is attributed to a mantle hot spot. We obtained new Sr, Nd, and Pb...
7,7'-Dihydroxy-8,8'-biquinolyl (azaBINOL) was prepared from 7-hydroxyquinoline via N,N-dimethyl O-quinol-7-yl carbamate by directed ortho-metallation followed by FeCl₃-mediated oxidative coupling of the 8-lithioquinoline intermediate. Saponification of the resulting dicarbamate provided crystalline (±)-azaBINOL in 56% overall yield. 6,6'-Bis(dimethylaminocarbonyl)-7,7'-dihydroxy-8,8´-biquinolyl was prepared from the same dicarbamate by a double anionic-Fries rearrangement in 43% yield. 7,7'-Bis(diethylamino-carbonyloxy)-6,6'-diiodo-8,8´-biquinolyl...
In this report, three studies are presented that aid in the development of drug discovery and their synthesis. In each, the importance of the marriage between computations and experiments is highlighted. Continued efforts in this vein are essential for future efforts towards improving human health.
The first case study investigated...
Members of the deltocephaline leafhopper genus Giprus Oman
live on grasses, primarily in the desert-scrub, chaparral, and
marine sand dune communities of western North America. Of 16
known species, 10 are undescribed. Recharacterization of the genus
results in exclusion of Laevicephalus incongruus Oman. Differentiation
of species is primarily dependent on...
Why are the fast Fourier transform and the fast
Hadamard transform fast? A transform can be computed by
multiplying a matrix times a vector, which normally requires 0(n²) operations. The matrices corresponding to
these transforms can be rearranged to eliminate redundant
computations resulting in O(nlogn) operations.
We investigate algebraic reasons...
Encryption is essential to the security of transactions and communications, but
the algorithms on which they rely might not be as secure as we all assume. In this
paper, we investigate the randomness of the discrete exponentiation function used
frequently in encryption. We show how we used exponential generating functions...
The general problem of classroom scheduling is well known to be NP-complete. A typical classroom scheduling problem is that of assigning students to a limited number of pieces of laboratory equipment. Frequently several identical pieces of equipment are available only at fixed hours and have limited access due to physical...
The FLEX/REFLEX paradigm is applied to the description of a computer program system. The paradigm is shown to be relevant and appropriate to computer program systems and to advantageously display and structure the general hierarchical characteristics of computer program systems. Program systems characterized in the paradigm are described both holistically...
The behavior of a metal vapor plasma arc in a vacuum arc remelting (VAR) furnace is believed to contribute to the formation of defects in reactive metal and super-alloy ingots. Industry standard instrumentation, which includes electric current and voltage measurements, can asses the stability of an arc but cannot predict...
Biologists need tools to see the structural relationships encoded in biological sequences (strings). The Walking Tree heuristics calculate some of these relationships. I have designed and implemented graphic presentations which allow the biologist (user) to see these relations. This thesis contains background information on the biological sequences and some background...
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...
Reinterpretation of the leafhopper tribe Scaphytopiini reveals it
to be primarily a New World taxon with only limited representation in
the Palearctic, Oriental and possibly Ethiopian regions. Approximately
75 species assigned to three genera are known from the United
States and Canada with at least another 75 species representing an...
Three distinct methods to achieve the stereoselective synthesis of carbon-carbon bonds were investigated, encompassing: (i) the formation of axially chiral biaryl molecules by enantioselective Suzuki cross-coupling, (ii) the synthesis of α-phenylalkylboronic esters by enantioselective chain extension, and (iii) the stereospecific synthesis of alkenes by eliminative cross-coupling of enantioenriched sp³-hybridized carbenoids....
The genus Coenonycha contains 30 described species of small to
medium sized scarabs. They are found in the arid and semi-arid
regions of western United States and northern Baja California. The
adults feed at night on several genera of xerophylous plants.
An examination of the male genitalia of the 19...
The stereospecific reagent-controlled homologation (StReCH) of boronic esters with enantioenriched carbenoid species generated in situ by the addition of organolithium initiators to stereodefined α-chloroalkyl aryl sulfoxides was previously reported. The reaction of an organolithium with an α-chloroalkyl aryl sulfoxide ostensibly generates an α-chloroalkyllithium via sulfoxide-lithium exchange; however, the true nature...
The bimolecular reaction of two carbenoid species resulting in the formation of a carbon-carbon double bond (pi-system), referred to herein as carbenoid eliminative cross-coupling (CEXC), involves a series of three fundamental steps: (i) ate-complex formation (transmetalation), (ii) 1,2-metalate rearrangement, and (iii) beta-elimination. All three steps are stereospecific and so the...
Xanthohumol [XN, (E)-6´-methoxy-3´-(3-methylbuten-2-yl)-2´,4´,4´´-trihydroxychalcone], the principal prenylated chalcone from hops, and its 2,3-dihydro- (DXN) and O6-desmethyl-2,3-dihydro- (DDXN) congeners, are of potential utility for the amelioration of metabolic syndrome; however, their complex bioactivity profiles cannot be properly studied and understood without access to appropriately produced synthetic materials.
In the first part of...
Traditional approaches for the direct preparation of alkenes are unable to fully control either the stereochemical configuration of the carbon-carbon double bond or else the regiochemistry of the substituents surrounding it. The recently introduced concept of carbenoid eliminative cross-coupling (CEXC) offers a remedy to these deficiencies by providing for a...
Ambifunctional axially chiral 2,2',6,6'-tetrasubstituted biphenyls containing nucleophilic (or basic) functional groups juxtaposed with hydrogen-bond donors were synthesized and their properties studied. Applications for the prepared biaryls as potential organocatalysts for enantioselective carbon-carbon bond forming reactions were examined. Processes investigated included: aldol, Michael, nitroaldol (Henry), and Baylis-Hillman reactions.
The novel amidoamine...
In previous work (Blakemore et al. Org. Lett. 2005, 7, 4721; Heterocycles 2006, 70, 609), successful elaborations of the lupine alkaloids (±)-α-isosparteine (dl-2) and (±)-β-isosparteine (dl-3) were realized from a common tetraoxobispidine precursor, 3,7-diallyl -2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (93). Herein, the tetraoxobispidine approach to lupine alkaloids was extended to a total synthesis of...
Two distinct strategies were explored for the enantioselective synthesis of α-heteroatom substituted alkyl boronic esters by stereoselective reagent-controlled homologation using transient chiral carbenoid reagents CHYMX (Y = heteroatom, X = nucleofuge, M = electrofuge). In the first case, a stereospecific reagent-controlled homologation (sStReCH) approach to α-alkoxyalkylboronates using α-metalated S,O- and...
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...
The synthesis of axially chiral polyfunctional derivatives of 8,8'-biquinolyl was explored and the catalytic action of appropriate derivative types investigated in three separate processes: (1) the silylcyanation of carbonyl groups and imines, (2) alkylation of a glycine Schiff-base via phase transfer-catalysis, and (3) direct amide bond formation from simple amines...
A comparison of the various endocrine glands, in addition to
other anatomical measurements, was made on 19 normal and 21
dwarf 2-3-month-old females and 20 normal and 20 dwarf 7-13-month-old females of the White Leghorn breed. At both ages, dwarfs
weighed significantly less and had significantly shorter shanks than
normals....
Benomyl-tolerant Botrytis cinerea was found in snap
bean fields throughout the Willamette Valley while no tolerant
isolates of Whetzelinia sclerotiorum were detected.
Thirty-five benomyl-tolerant isolates of B. cinerea had
slower radial growth rates than eighteen benomyl-sensitive
isolates. Sporulation of an aggressive tolerant isolate
was not stimulated when grown on benomyl-treated...
A study of the immature stages of the subfamily Troginae in
North America was conducted from the spring of 1963 through the
spring of 1965, Larvae of Trox and Omorgus were easily reared in
the laboratory, but all attempts to rear the larvae of Glaresis were
unsuccessful,
The suberosus group,...
My work on computing complex catalyzed organic transformations reveals that only a few subtle chemical factors, e.g. non-classical hydrogen bonding, (hyper)conjugation and steric effects, common across different catalyst manifolds are critical for catalysis and selectivity. Rational manipulation and exploitation of these factors has led to improved catalyst designs, which has...
Chalaniline A, an unusual xanthone-like aminofulvene with modest cytotoxicity, and chalaniline B [1-anilino-2,8-dihydroxy-3-(hydroxymethyl)xanthone], an antibacterial aminoxanthone, were previously isolated by Loesgen and coworkers from vorinostat-treated Chalara sp. 6661. Of note, the anilino moiety found within both chalaniline structures originates from biotransformation of the HDAC inhibitor vorinostat (SAHA, suberanilohydroxamic acid) by...
Complex organic transformations, such as the addition of pyrrole to ketene using planar chiral organocatalyst (*PPY), the four-component anhydride- Manniach reactions, and the site-selective desymmetrization of meso-1,2-diol, are remarkable synthetic reactions that provide high yield and high selectivity. However, the exact mechanism and origins of stereocontrol for theses synthetic organic...
My work has focused on using density functional theory to elucidate mechanisms of organocatalytic and transition metal catalyzed reactions by considering competing mechanisms. In each of the three presented studies computational investigation complemented experimental work by predicting stereoselectivity or revealing origins of stereo, regio, or chemoselectivity.
A study on the...
An intramolecular variant of the modified-Julia olefination was demonstrated by the synthesis of α,β-unsaturated lactones in a mild and (Z)-selective fashion. The lynchpin reagent (benzothiazol-2-sulfonyl) acetic acid was synthesized in a straightforward fashion in 86% overall yield from commercially available 2-mercaptobenzothiazole via conversion to ethyl (benzothiazol-2-ylthio)acetate by base mediated alkylation...
Microchannel process technology (MPT) offers several advantages to the field of nanomanufacturing: 1) improved process control over very short time intervals owing to shorter diffusional distances; and 2) reduced reactor size due to high surface area to volume ratios and enhanced heat and mass transfer. The objective of this thesis...
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Brian K. Paul
Microchannel process technology (MPT) offers several advantages to the field
The practice of green infrastructure is synonymous with collaborative partnerships. Expertise from engineers, land care professionals, planners, and natural resource consultants are often required for successful project implementation. Traditionally, these professionals perform their responsibilities in their disciplinary “silos,” but this evolving area of sustainable development is creating a demand for...
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Paul Ries Jenna H. Tilt
The practice of green infrastructure is synonymous with
There have been years of stalled K-12 school finance reform efforts in Idaho, yet it was unclear what key Idaho education interest groups currently thought about how Idaho funds its public schools. Therefore, this project explored the institutional perspectives and beliefs of K-12 Idaho education stakeholders regarding the Idaho K-12...
In Part I, (4S,5R)-4,5-dimethyl-4-phenylcyclohex-2-enone (19a) was prepared in 73% yield with high enantio- and diastereo-selectivity (er > 98:2, dr > 20:1) on a multigram scale by a Yamada-Otani condensation between (E)-pent-3-en-2-one and 2-phenylpropanal catalyzed by a sulfonimide derivative of (S)-proline (18, HuaCat®). Synthetically useful transformations of the cyclohexenone product 19a...
Several experiments were carried out on Coturnix coturnix
japonica to investigate the effect of selection for growth on a protein
deficient ration. A level of 27% protein was found to be optimum for
three different strains and 17.8% was the lowest protein level used
that allowed for growth and accordingly...
Theoretical breaking criteria for progressive surface gravity
waves are examined, and laboratory and field experiments concerned
with breaking waves are reviewed with respect to the testing of these
breaking criteria. The measurements of Komar and Simmons are
presented here for the first time. Only three theoretical breaking
criteria have been...
Advances in plant construction within the energy and chemical process industries require inexpensive process intensification (PI) technology as a means to reduce plant size for enabling modular construction. One form of PI is microchannel process technology where arrays of microchannels, having hydraulic diameters on the order of 0.1 to 1...
The records of a population of sex-linked dwarf layers
at the Oregon State Agricultural Experiment Station subjected
to an accelerated selection for hen-housed egg production at
40 weeks of age for a period of over 11 years were analyzed
for selection response, and for the estimation of genetic
parameters. The...