Direct Liquid Chromatographic Separation of Enantiomers of Phthalides, Phthalimidines and Related Compounds on Chiral Stationary Phases

The enantiomers of a diverse series of 3-arylphthalides are separable by high performance liquid chromatography on chiral stationary phases (CSPs) derived from the N-3,5-dinitrobenzamides of (S)-leucine or (R)-phenylglycine covalently bonded to aminopropyl silanized silica. A chiral recognition model for the separation of phthalide enantiomers has been formulated based on the observed chromatographic behavior of these phthalides. Assignment of elution orders based on the a priori model proposed are consistent with those ultimately determined by independent chemical and spectroscopic means. A phthalide structurally optimized to maximize the chromatographic separability of its enantiomers on the aforementioned CSPs is incorporated into a phthalide-based CSP which has proven to be effective for the separation of enantiomers of numerous analytes. The chromatographic behavior of a variety of 3-arylphthalimidines and their corresponding ureide derivatives on the amino acid CSPs, as well as a novel procedure for C-3 alkylation without N-2 alkylation of these phthalimidines via conversion to the ureide derivatives, is described. Alkylation of certain enantiomerically pure ureides affords enantiomerically enriched products owing to the self-immolative transfer of chirality from central to axial, back to central chirality. Factors affecting this process are discussed.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Sowin, Thomas Joseph

• Chemistry, Organic

Identifier

(UMI)AAI8711882

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70365