Assessment of the host potential of TETROL [(+)-(2R,3R)-1,1,4,4- tetraphenylbutane-1,2,3,4-TETROL] for the separation of isomers and related compounds
- Authors: Dorfling, Sasha-Lee
- Date: 2018
- Subjects: Chemistry, Organic , Thermal analysis Hydrogen bonding
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/22060 , vital:29817
- Description: In this study, we investigated the potential of a host compound, (+)-(2R,3R)-1,1,4,4- tetraphenylbutane-1,2,3,4-tetrol (TETROL), for use in the separation of isomers and related compounds using host-guest chemistry. The synthesis of this host was carried out using a standard Grignard procedure, reacting naturally-occurring optically active tartaric acid with phenylmagnesium bromide. The feasibility of this host for separating isomers and structurally-related compounds was investigated by recrystallizing it from various potential cyclic, aromatic and aliphatic guest compounds. The extent of host inclusion and guest separation were determined using 1H-NMR spectroscopy and GCMS analyses. Competition studies were conducted to establish the selectivity of TETROL for the various guest species and whether this host would be able to discriminate between them. In this instance, the host was recrystallized from equimolar amounts of binary, ternary, quaternary or quinary mixtures of the guests present in each target study. Subsequent binary or ternary competitions were conducted where the molar ratios of the guest species were varied beyond equimolar, and the guest selectivity of TETROL thus evaluated by means of selectivity profiles. Further analyses included single crystal X-ray diffraction (SCXRD), thermal analysis and Hirshfeld surface analysis. Any crystalline inclusion complex formed between host and guest, with suitable crystal quality, was analysed using SCXRD in order to determine the nature of any significant host–guest interactions present. Thermogravimetric and differential scanning calorimetry experiments provided further insight into complex stability by analysing the thermal events experienced by the complexes as they were heated at 10 °C/min. The data obtained from Hirshfeld surface analyses were used to determine whether host selectivity and/or thermal stability of the complexes were related to the number and types of interactions, observed from SCXRD, between host and guest. The ability of TETROL to discriminate between related compounds was favourable. This host proved to have selective preference for aniline over its methylated derivatives, N-methylaniline and N,N-dimethylaniline. It was also selective for cyclohexylamine over cyclohexanol and cyclohexanone, and discriminated against the pyridine, piperidine and dioxane heterocyclics in favour of morpholine. Furthermore, this host was successful in the selective separation of isomers; for example, it selectively showed discrimination between the three toluidine isomers (p-toluidine > m-toluidine > o-toluidine) and the cresols (p-cresol > m-cresol > o-cresol). Each guest mixture was selected based on data from experiments using either the industrial significance of its separation or because the mixture would add to the knowledge base of the host compound’s preferences and selectivities. In a separate study, TETROL and its derivative, (–)-(2R,3R)-2,3-dimethoxy-1,1,4,4- tetraphenylbutane-1,4-diol (DMT), were also allowed to compete for the inclusion of the guest cyclohexanone, where TETROL demonstrated superior ability. This host, in addition, showed potential for the separation of cis- and trans- 2-methylcyclohexanol.
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- Date Issued: 2018
Enantioselective transformations using tetrol as a chiral mediator
- Authors: Dorfling, Sasha-Lee
- Date: 2015
- Subjects: Enantioselective catalysis , Trichothecenes , Catalysts , Titanium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10445 , http://hdl.handle.net/10948/d1021195
- Description: (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) and its derivatives were reacted with varying molar ratios of titanium isopropoxide (2:1, 1:1 and 1:2 tetraol:titanium isopropoxide) in an attempt to prepare potential titanium-based tetraol catalysts for enantioselective transformations. In each case, infrared and HNMR spectra suggested that the product was formed. We tentatively proposed that the structure of the catalyst was a spiro-type, but we could not determine conclusively what its exact structure was, despite using numerous techniques at our disposal (molecular modelling calculations, H NMR and IR spectroscopy, thermal analyses, powder diffraction, and single crystal X-ray diffraction). The catalyst and derivatives thereof were able to act catalytically for the enantioselective additions of diethylzinc compounds to aldehydes. The effects of temperature and solvent were investigated, and toluene and -78 °C were selected as optimal from the results obtained. (The reaction could, however, not be maintained at this low temperature for extended periods due to the fact that we did not have, at our disposal, the correct equipment. Each 16 h reaction was thus allowed to reach room temperature in each case.) The selectivity for the product 1-phenylpropan-1-ol (when benzaldehyde was the starting aldehyde) varied depending on the nature of the aryl substituents of the titanium-based catalyst. Using 0.2 molar equivalents of the chiral titanates, the highest selectivity was 42 percent (e.e.), but only when excess Ti(O-i-Pr)4 had been added to the reaction mixture. This was achieved with the tetra(ortho-methoxyphenyl)-TETROLate derivative. TETROL and its derivatives were also successful in metal-free catalysis where higher conversions and selectivities were observed, compared to when these were complexed to titanium. The highest selectivity was 70 percent (e.e.), achieved with the tetra(ortho-methylphenyl)TETROL derivative.
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- Date Issued: 2015