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...
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...
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...
The synthesis of 3,3'-diphenylbenzopinacol was carried out both by means of the Grignard reaction between m-diphenyl magnesium iodide and benzil, and by reduction of m-phenyl benzophenone. The pinacol was rearranged and the products analyzed. The migration aptitude of m-biphenyl was determined to be 1.5. Attempts to prepare 3,3'-diphenyl-4,4'-dimethylbenzopinacol were unsuccessful....
A sensitive, selective, rapid analytical method based on large-volume injection (LVI)
liquid chromatography/ tandem mass spectrometry was developed using
commercially-available hardware that eliminates the need for either off-line or on-line
solid phase extraction. Centrifugation followed by the direct injection of 1,800 µL
was used for the quantification of illicit drugs,...
The variegated aqueous chemistries of metal cations are applied to the design and synthesis of non-toxic solution precursors suitable for additive printing of large-area oxide electronics. Polycondensation behaviors of aqueous Al+3 and PO4 +3 are manipulated in the deposition of atomically smooth amorphous aluminum oxide phosphate (AlPO) dielectric films. AlPO...
The use of semi-volatile organic compounds (SOCs) as molecular markers to identify the contributions of regional and long-range atmospheric transport, as well as current and historic sources, and contaminant deposition in remote ecosystems of the Western U.S. was investigated. Trans-Pacific air masses influenced by Siberian biomass burning events had elevated...
Patterning of metal oxides typically involves a multi step process, involving
depositing a resist, patterning that resist with some form of lithography, etching the
oxide through the resist, and finally removing. This process can be simplified if the
resist is removed and replaced with a metal oxide that can be...
The preparation and characterization of thin film oxides and chalcogenides by pulsed laser deposition (PLD) is presented. An overview of fundamental PLD concepts are presented and are followed by a description implementation and development of the PLD systems at OSU. We present the results of thin film growth of high...
Many D2d-symmetric 2,2',6,6'-tetrasubstituted biphenyls are
readily prepared via net oxidative dimerization of appropriate
1,3-disubstituted benzenes. Conversion of such proprochiral
compounds to useful C2-symmetric chiral biphenyls requires
formal replacement of two substituents on opposing aryl ring
units with alternate groups. This under exploited
desymmetrization tactic has been demonstrated for the
generation...