Synthesis of chiral ketopinic acid-derived catalysts and their evaluation in asymmetric transformations
- Authors: Hassan, Yusuf
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/550 , vital:19969
- Description: Four new (+)-ketopinic acid-derived Mn(III) complexes, three of which possess pseudo C2- symmetry, were synthesised as chiral catalyst candidates. The ligands were prepared by refluxing (+)-ketopinic acid with ethane-1,2-diamine, the resolved (R,R)- and (S,S)-1,2-diaminocyclohexanes, and 1,2-diaminobenzene in chloroform. Treatment of the ligands with manganese(II) acetate tetrahydrate in refluxing ethanol afforded the respective complexes as brown amorphous powders. Characterisation of the ligands and the corresponding complexes was achieved using 1-D and 2-D NMR, IR spectroscopy, and elemental analysis. Various homogeneous asymmetric transformations, were investigated using these four complexes, viz., aldol, and Baylis-Hillman reactions, aza-Michael addition of piperidine to the Baylis-Hillman adducts, epoxidation, and ketone and imine reduction. Asymmetric aldol reactions of benzaldehyde with the aryl ketones, acetophenone, propiophenone, -tetralone, 4-nitroacetophenone, and 4-methoxyacetophenone, conducted in the presence of 10 mole % of the chiral catalysts, afforded enantioselectivities of up to 99% e.e. Asymmetric Baylis-Hillman reactions of methyl- and tert-butyl acrylates with pyridine-2- carbaldehyde, 6-methylpyridine-2-carbaldehyde, 5-chlorosalicylaldehyde, benzaldehyde, 4-chlorobenzaldehyde, and 2-nitrobenzaldehyde were conducted in the presence of catalyst 139 (10 mole %) to afford enantioselectivities of up to 44% e.e. Aza-Michael addition of piperidine to racemic Baylis- Hillman adducts in the presence of the catalyst 139 (10 mole %) was found to proceed with diastereoselectivities of up to 91% d.e. Asymmetric epoxidation of trans-methyl styrene, styrene, trans-stilbene, cis-stilbene, and indene, using a 5 mole % chiral catalyst loading and m-CPBA as the oxygen source, gave enantioselectivities of up to 32 % e.e. Asymmetric reductions of acetophenone, 3-chloropropiophenone, 4-hydroxyacetophenone, -tetralone, and 2-hydroxy-1-acetonapthone were investigated using NaBH4 as the reducing agent and a 10 mole % loading of the chiral catalysts. A stereoselectivity of 68% e.e. was obtained in the reduction of acetophenone, but attempts to reduce the selected imines to the corresponding chiral amines proved to be unsuccessful — even in the absence of the catalysts. It thus became apparent that the catalytic version of the reaction was not feasible.
- Full Text:
- Date Issued: 2016
- Authors: Hassan, Yusuf
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/550 , vital:19969
- Description: Four new (+)-ketopinic acid-derived Mn(III) complexes, three of which possess pseudo C2- symmetry, were synthesised as chiral catalyst candidates. The ligands were prepared by refluxing (+)-ketopinic acid with ethane-1,2-diamine, the resolved (R,R)- and (S,S)-1,2-diaminocyclohexanes, and 1,2-diaminobenzene in chloroform. Treatment of the ligands with manganese(II) acetate tetrahydrate in refluxing ethanol afforded the respective complexes as brown amorphous powders. Characterisation of the ligands and the corresponding complexes was achieved using 1-D and 2-D NMR, IR spectroscopy, and elemental analysis. Various homogeneous asymmetric transformations, were investigated using these four complexes, viz., aldol, and Baylis-Hillman reactions, aza-Michael addition of piperidine to the Baylis-Hillman adducts, epoxidation, and ketone and imine reduction. Asymmetric aldol reactions of benzaldehyde with the aryl ketones, acetophenone, propiophenone, -tetralone, 4-nitroacetophenone, and 4-methoxyacetophenone, conducted in the presence of 10 mole % of the chiral catalysts, afforded enantioselectivities of up to 99% e.e. Asymmetric Baylis-Hillman reactions of methyl- and tert-butyl acrylates with pyridine-2- carbaldehyde, 6-methylpyridine-2-carbaldehyde, 5-chlorosalicylaldehyde, benzaldehyde, 4-chlorobenzaldehyde, and 2-nitrobenzaldehyde were conducted in the presence of catalyst 139 (10 mole %) to afford enantioselectivities of up to 44% e.e. Aza-Michael addition of piperidine to racemic Baylis- Hillman adducts in the presence of the catalyst 139 (10 mole %) was found to proceed with diastereoselectivities of up to 91% d.e. Asymmetric epoxidation of trans-methyl styrene, styrene, trans-stilbene, cis-stilbene, and indene, using a 5 mole % chiral catalyst loading and m-CPBA as the oxygen source, gave enantioselectivities of up to 32 % e.e. Asymmetric reductions of acetophenone, 3-chloropropiophenone, 4-hydroxyacetophenone, -tetralone, and 2-hydroxy-1-acetonapthone were investigated using NaBH4 as the reducing agent and a 10 mole % loading of the chiral catalysts. A stereoselectivity of 68% e.e. was obtained in the reduction of acetophenone, but attempts to reduce the selected imines to the corresponding chiral amines proved to be unsuccessful — even in the absence of the catalysts. It thus became apparent that the catalytic version of the reaction was not feasible.
- Full Text:
- Date Issued: 2016
The design and synthesis of multidentate N-heterocyclic carbenes as metathesis catalyst ligands
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
- Authors: Truscott, Byron John
- Date: 2011
- Subjects: Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4304 , http://hdl.handle.net/10962/d1004962 , Carbenes (Methylene compounds) , Heterocyclic compounds , Ligands , Ligands -- Design , Metathesis (Chemistry) , Catalysis
- Description: This study has focused on the design and preparation of bi– and tridentate N–Heterocyclic Carbene (NHC) ligands in order to investigate the effect of a multidentate approach to the formation, stability and catalytic activity of coordination complexes. Chapters 1 – 3 provide background information of relevant catalysis, carbene and coordination chemistry, followed by previous work performed within our research group. In Chapter 4 attention is given to the synthetic aspects of the research conducted, comprising two distinct approaches to the preparation of unsymmetrical saturated and unsaturated NHCs. Firstly, an investigation of the saturated NHC ligands yielded three novel, unsymmetrical pro–ligands, viz., two halopropyl imidazolinium salts and a bidentate hydroxypropyl imidazolinium salt. Secondly, eight imidazolium salts have been generated, including a hydroxypropyl analogue and novel decyl and tridentate malonyl derivatives. These compounds were prepared using microwave–assisted methodology for the alkylation of N– mesitylimidazole – an approach that drastically reduced reaction times (from 8 hours – 7 days to ca. 0.5 – 2 hours) and facilitated isolation of the imidazolium salts. Many of the compounds prepared in this study are novel and were fully characterized using HRMS and 1– and 2–D NMR analysis. Coordination studies using a selection of the prepared pro–ligands afforded an alkoxy–NHC silver derivative and four novel Ru–complexes, viz., Grubbs II–type Ru–complexes containing:– chloropropyl imidazolinylidene; propenyl imidazolylidene; and bidentate alkoxypropyl imidazolylidene ligands. Furthermore, a well–defined benzyl mesitylimidazolylidene Ru–complex has been isolated, which exhibited good stability in air. DFT–level geometry–optimization studies, using the Accelrys DMol3 package have given valuable insights into the likely geometries of the prepared and putative catalysts.
- Full Text:
- Date Issued: 2011
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