Elucidating structures of novel compounds and investigation of new reactions are two
tasks that experimental organic chemists address on a frequent basis. The pursuit of these
objectives can be rigorous and time-consuming. Of the methods employed in elucidating
the structure of novel compounds, nuclear magnetic resonance (NMR) is by far the most
widely applied. Investigation into new reactions may require any number of techniques to
understand the reaction scope, kinetics, optimal conditions, mechanisms, etc. In both cases,
the use of computational methods is well-suited to augment the experimentalist's data to
guide and understand the system being investigated.
A protocol for facilitating computational prediction of NMR chemical shifts was developed.
Application to a set of natural products previously evaluated against computed
NMR shifts, showed improved accuracy, through analysis of the corrected mean-absolute
error (CMAE). The protocol was further employed successfully to aid in analysis of experimental
spectra for compounds synthesized by collaborators where multiple diastereomers
were possible. Graphing templates were also created to allow for rapid inspection of possible
structures without more in-depth statistical analysis.
Thermodynamic and mechanistic analysis on the formation and reaction of benzyne was
also performed. Thermodynamic restrictions on the ring-size of fused benzynocycloalkanes
were investigated. Additionally, analysis of the energetics and transition state geometries
for small-molecule trapping (both intra and intermolecular) of benzyne are discussed.
University of Minnesota M.S. thesis. January 2013. Major: Chemistry. Advisor: Thomas R. Hoye. 1 computer file (PDF); ix, 247 pages.
Marell, Daniel Joshua.
Development and testing of a protocol for computational prediction of 1H and 13C NMR chemical shifts and thermochemistry and reaction analysis of benzyne formation and trapping.
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