A chiral tag study of the absolute configuration of camphor

Smart, Taylor

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https://hdl.handle.net/2142/97105 Copy

Description

Title

A chiral tag study of the absolute configuration of camphor

Author(s)

Smart, Taylor

Contributor(s)

• Pate, Brooks
• West, Channing
• Mayer, Kevin J.
• Holdren, Martin S.
• Evangelisti, Luca
• Pratt, David

Issue Date

2017-06-21

Keyword(s)

Chirality-sensitive spectroscopy

Abstract

The chiral tagging method for rotational spectroscopy uses an established approach in chiral analysis of creating a complex with an enantiopure tag so that enantiomers of the molecule of interest are converted to diastereomer complexes. Since the diastereomers have distinct structure, they give distinguishable rotational spectra. Camphor was chosen as an example for the chiral tag method because it has spectral properties that could pose challenges to the use of three wave mixing rotational spectroscopy to establish absolute configuration. Specifically, one of the dipole moment components of camphor is small making three wave mixing measurements challenging and placing high accuracy requirements on computational chemistry for calculating the dipole moment direction in the principal axis system. The chiral tag measurements of camphor used the hydrogen bond donor 3-butyn-2-ol. Quantum chemistry calculations using the B3LYP-D3BJ method and the def2TZVP basis set identified 7 low energy isomers of the chiral complex. The two lowest energy complexes of the homochiral and heterochiral complexes are observed in a measurement using racemic tag. Absolute configuration is confirmed by the use of an enantiopure tag sample. Spectra with $^{13}$C-sensitivity were acquired so that the carbon substitution structure of the complex could be obtained to provide a structure of camphor with correct stereochemistry. The chiral tag complex spectra can also be used to estimate the enantiomeric excess of the sample and analysis of the broadband spectrum indicates that the sample enantiopurity is higher than 99.5%. The structure of the complex is analyzed to determine the extent of geometry modification that occurs upon formation of the complex. These results show that initial isomer searches with fixed geometries will be accurate. The reduction in computation time from fixed geometry assumptions will be discussed.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/97105

DOI

https://doi.org/10.15278/isms.2017.WG02

Copyright and License Information

Copyright 2017 Taylor Smart

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