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 yields of 235 projectile-like and target-like fragments from the interaction of ¹³⁶Xe with a thick target of ²⁰⁸Pb at a center-of-mass energy, E[subscript cm], of 450 MeV were measured using γ-γ-γ coincidence data from Gammasphere and off-line γ-ray spectroscopy. The results give an expansive picture of the production cross...
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...
The synthesis of superheavy element evaporation residues is described by the product of the capture cross section, fusion probability, and survival probability. Capture cross sections are moderately well known. The fusion probability is the least known with many uncertainties. The formalism for the survival probability is known, but the parameters...
As part of the continuing investigation of the thermal cis- 1, 3, 5-hexatriene to 1,3-cyclohexadiene rearrangement, four new trienes and a cross-conjugated pentaene have been prepared and their thermal reactions studied. A new route to the synthesis of highly substituted trienes has been developed. The synthesis of three of these...
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...
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 development and applications of a 0.2 cm⁻¹ resolution
Nd-YAG laser powered coherent anti-Stokes Raman
spectroscopy, CARS, spectrometer for gas phase studies is
chronicled in this thesis. Applications including CARS
lineshape analysis, resonant CARS, and CARS of transient
species and excited state molecules is reported.
The intensity of the signal...
A specially designed gas chromatograph with both TCD and FID has
been tested for the measurement of the diffusion coefficients of methane and propane in helium. Knox's arrested elution technique(⁴) was used and yielded a value of 0.6431 cm²/sec averaged with the value
obtained by Yang and Hawkes(⁷). Values of...